CN100523038C - Polyurethane with shape memory property, composition containing it and shape memory fabric prepared therefrom - Google Patents

Polyurethane with shape memory property, composition containing it and shape memory fabric prepared therefrom Download PDF

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Publication number
CN100523038C
CN100523038C CNB2004100025522A CN200410002552A CN100523038C CN 100523038 C CN100523038 C CN 100523038C CN B2004100025522 A CNB2004100025522 A CN B2004100025522A CN 200410002552 A CN200410002552 A CN 200410002552A CN 100523038 C CN100523038 C CN 100523038C
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preparation
urethane
agent
shape memory
diisocyanate
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CN1648143A (en
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胡金莲
杨卓鸿
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Hong Kong Polytechnic University HKPU
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Hong Kong Polytechnic University HKPU
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Abstract

The said polyurethane is prepared through preparing polymer with diisocyanate, hydroxyl-containing oligomer, chain expander with active hydrogen radical and chain expander with carboxylic radical, neutralizer with alkali radical, blocking agent, cross-linking agent and optional catalyst in certain proportion; and subsequent reaction in water to obtain polymer. The polyurethane features the blocking diisocyanate radical and hydroxyl radical and thus shape converting temperature of -30 deg.c to 100 deg.c. In temperature higher than the shape converting temperature, the polyurethane may have its shape converted; in temperature lower than the shape converting temperature, the polyurethane is unchanged in shape; and the polyurethane heated to the temperature higher than the shape converting temperature will restore original shape.

Description

Have the urethane of shape memory, the composition that contains it and shape memory fabrics
Technical field
The present invention relates to a kind of urethane and application in the preparation shape memory fabrics thereof with shape memory.More specifically, the present invention relates to have the urethane, water-based shape memory polyurethane composition and method of making the same, shape memory fabrics and preparation method thereof of shape memory.
Background technology
Usually, has foam materials that the urethane of shape memory makes be widely used (day flat 2-113016 of disclosure special permission communique, 1990, Mitsubishi Heavy Industry Ltd.).Shape memory polyurethane has the big and thermal insulation of deformation amount of recovery, and these characteristics are widely applied in the extensive stock.These foaies can under certain shape need and under certain model by post forming.The shape-memory polymer of moulding changes shape being higher than under its shape memory transition temperature but being lower than under the rheology temperature, when polymkeric substance is cooled to be lower than the shape memory transition temperature with the state after changing, and the shape of change just fixing.The method of utilizing of shape memory is thereby that the shape that will change is heated to above shape memory transition temperature recovery virgin state.That is to say that shape-memory polymer finalizes the design in certain model deformation in certain temperature variation.
Open WO01/07499 of PCT international application and the open CN1361799A of Chinese patent application disclose the preparation method of shape memory polyurethane or polyurethane-urea polymers, its second-order transition temperature is 20~100 ℃ of scopes, flexible polyurethane section monomer adopts the polysiloxane macromolecule dihydric alcohol, the monomer cost is higher, is mainly used in medical device.Also have the shape-memory material of some patents and bibliographical information polyurethane-base in addition, they have certain purposes at aspects such as toy, medical treatment, automobiles.
Wrinkle proofing is the important postfinishing process of fabric, and traditional crease proofing agent is mainly N-methylol amide compounds, can discharge a large amount of formaldehyde when textile finishing; Fabric after the arrangement, deposit or wearing process in, also can decompose or discharge formaldehyde.At present the formaldehydeless finishing agent of exploitation mainly contain Resins, epoxy, double hydroxyethyl sulfone, dimethyl urea oxalic dialdehyde, 1,2,3,4-tetracarboxylic acid butane (BTCA) etc.But what have application prospect most is 1,2,3,4-tetracarboxylic acid butane (BTCA), and United States Patent (USP) 4,975 has disclosed polycarboxylic acid in 209,4,820,307 and 5,221,285 and be linked to the wrinkle resistant effect of playing on the fabric under the effect of catalyzer.But crosslinked polycarboxylic acid has reduced the tear strength of fabric, and the arrangement cost is too high.
We find that water-based shape memory polyurethane composition is applied on textiles and the clothing, has shape memory effect in the research.Up to the present, go back the report of Shang Weijian so far about water-based shape memory polyurethane composition and relevant shape memory fabrics.Further, up to the present, home and overseas is not also about preparing argumentation, report and the patent of water-based shape memory polyurethane by the introduction carboxylic group.
For overcoming the limitation of prior art, and at traditional new understanding of crease-resistant notion proposition, the object of the present invention is to provide fabric with shape memory function, this shape memory fabrics has good wrinkle resistant function on the shape memory transition temperature, the various wrinkle that especially can recover to produce in water washing process promptly recover its original-shape and keep its elasticity simultaneously.This fabric is put in order or is applied and get via water-based shape memory polyurethane composition.
Summary of the invention
For achieving the above object, the present invention at first provides a kind of urethane, and its weight-average molecular weight is characterized in that between 10000 to 100000 this urethane is that the prepolymer that following component reaction prepares is continued the resulting polymkeric substance of reaction in water:
1) vulcabond;
2) hydroxyl oligopolymer;
3) contain the chainextender and the carboxylic chainextender of active hydrogen group;
4) contain the neutralizing agent of basic group;
5) end-capping reagent;
6) linking agent, and
7) Ren Xuan catalyzer,
It is characterized in that isocyano and hydroxyl (NCO/OH=0.8~1.6) end-blocking of described urethane with different molal quantities, and described component molar ratio is, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: linking agent: catalyzer=0.8~1.6:0.2~0.8:0.4~1:0.2~0.6:0~1.2:0~0.4:0~0.02, described urethane has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.
The present invention further provides a kind of polyurethane composition, it contains aforesaid urethane and water, and the solid content of described composition is 5%-50% (weight).
The present invention also provides the preparation method of aforesaid urethane, comprises the steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated;
B) in reaction process, add chainextender and the carboxylic chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) gained prepolymer in the step d) is scattered in the water, makes it to continue reaction.
The present invention further provides a kind of preparation method of shape memory fabrics, comprised using to comprise substrate fabric is put in order as the finishing composition of aforesaid urethane.
The present invention also provides the preparation method of another shape memory fabrics, comprises using the coating-forming agent that contains aforesaid urethane that substrate fabric is applied.
The present invention further provides a kind of shape memory fabrics, it comprises substrate fabric and aforesaid urethane.
An advantage of the present invention is that described shape memory polyurethane has improved mechanical property, the transparency, biologically stable, resistance to deterioration, oxidation-resistance, anti-time property, formaldehydeless release and environmentally friendly property.
Another advantage of the present invention is, the production technique of the shape memory fabrics that adopts (comprising arrangement and coating) is compared with at present common postfinishing process, step without any complexity, and owing to do not adopt strongly acidic catalyst and long-time high temperature to bake and bank up with earth, to the brute force and the not damage of hand feel and drape of fabric.
Advantage of the present invention more is embodied in described shape memory fabrics can recover the folding line that produces in dress or the folding process in 30-100 ℃ of warm air or hot water, be returned to the original-shape of fabric.Described shape memory fabrics can the end capped isocyano of deblocking in the process of baking and banking up with earth, and makes it self to take place crosslinked or reacts the shape memory function of reinforced fabric, water-wash resistance and chemical-resistant with reactive group on the fabric fibre.Described shape memory fabrics has the characteristics of fabric form memory reservation, wrinkle resistant, shrinkproof typing, no strength loss, hand feel and drape, moisture-penetrable ventilated property, environmental friendliness, formaldehydeless release.The fabrics feel soft of arrangement can keep the primary state substantially.No matter fabric produces fold or distortion when placing or wearing for a long time, this fabric is heated to more than the shape memory transition temperature, and fabric can be relatively easy to return to the virgin state that it remembers and eliminate the fold or the distortion of generation.Therefore can be used as face, the back of the body, the sleeve of shirt through the fabric of this kind method arrangement.In a word, the fabric of handling through different arrangement prescriptions can use at the different sites of shirt, has very high using value.
Embodiment
The invention provides a kind of urethane with shape memory, its weight-average molecular weight is characterized in that between 10000 to 100000 this urethane is that the prepolymer that following component reaction prepares is continued the resulting polymkeric substance of reaction in water:
1) vulcabond;
2) hydroxyl oligopolymer;
3) contain the chainextender and the carboxylic chainextender of active hydrogen group;
4) contain the neutralizing agent of basic group;
5) end-capping reagent;
6) linking agent, and
7) Ren Xuan catalyzer,
It is characterized in that isocyano and hydroxyl (NCO/OH=0.8~1.6) end-blocking of described urethane with different molal quantities, and described component molar ratio is, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: linking agent: catalyzer=0.8~1.6:0.2~0.8:0.4~1:0.2~0.6:0~1.2:0~0.4:0~0.02, described urethane has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.
The ratio of preferred vulcabond and hydroxyl oligopolymer is 1.1-2.5.Wherein, preferably, described vulcabond can be selected from aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and composition thereof, described aliphatic diisocyanate can be selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate, described aromatic diisocyanate can be selected from 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate; The optional autopolyester polyvalent alcohol of described hydroxyl oligopolymer, polyether glycol, polycarbonate, polycaprolactone and composition thereof; The described chainextender that contains active hydrogen group can be selected from 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane; Described carboxylic chainextender is a dimethylol propionic acid; Described neutralizing agent can be selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, and in described neutralizing agent and the urethane ratio of contained carboxyl at 1:0.5 between the 1:1.2; Described linking agent is selected from water miscible small molecules polyvalent alcohol and polyhydric alcohol amine; Described linking agent can be selected from glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine; Described end-capping reagent is selected from Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
The present invention also provides a kind of polyurethane composition with shape memory, it comprises aforesaid urethane and water, the solid content of described composition is 5%-50% (weight), preferred described composition do not contain surpass 30% (weight) can be miscible with water organic solvent, more preferably described composition does not contain any organic solvent.
The present invention also provides the preparation method of aforesaid urethane, comprises the steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated;
B) in reaction process, add chainextender and the carboxylic chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) gained prepolymer in the step d) is scattered in the water, makes it to continue reaction.
The invention provides a kind of preparation method of shape memory fabrics, comprise and use the finishing composition that comprises aforesaid urethane that substrate fabric is put in order.
In one embodiment of the invention, described adjustment method comprises the steps: a) to pad substrate fabric with finishing composition; B) oven dry; And c) bake and bank up with earth, preferably include following steps: a) pad substrate fabric with finishing composition, two soak two rolls mangle expression 100%~150%; B) 80~90 ℃ of oven dry 1~3 minute; And c) baked and banked up with earth 1~3 minute at 140~170 ℃.
In one embodiment of the invention, described finishing composition comprises following composition: the urethane of 4-10% weight part; The softening agent of 1-3% weight part; Permeate agent with the 1-3% weight part.
The present invention also provides the preparation method of another kind of shape memory fabrics, comprise and use the coating-forming agent that contains aforesaid urethane that substrate fabric is applied, handle the substrate fabric that has applied preferred also comprising with flocculation agent, wherein carries out coated with blade coating, roller coating or impregnation method.Preferably wherein in the used coating agent solid content be 10-60 weight %, preferred 20-50 weight % counts 10-200g/m to cause on the fabric coating amount to do weightening finish 2The agent of amount applying coating, preferred 20-100g/m 2
Preferably, wherein used flocculation agent is selected from metal-salts such as aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, sylvite, perhaps be selected from organic or inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, perhaps be selected from the mixture that described material constitutes, the concentration of wherein said flocculation agent is 0.5-40% by weight, is preferably 1-20%; The substrate fabric that has wherein applied treatment time in flocculation agent is 10 seconds to 10 minutes, is preferably 1 to 5 minute.
The present invention also provides a kind of shape memory fabrics, and it comprises substrate fabric and aforesaid urethane.
Used substrate fabric is textile fibres or non-woven fibre in aforesaid method and fabric, and described fiber is preferably the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers.
The shape memory polyurethane that has elasticity with conventional shape-memory urethane more than the shape memory transition point and generally obtain is with hydroxy-end capped different, shape memory polyurethane of the present invention is with the isocyano and hydroxyl (NCO/OH=0.8~1.6) end-blocking of different molal quantities, weight-average molecular weight is between 10000 to 100000, has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.The tensional modulus of the tensional modulus of this shape memory polyurethane when being higher than 10 ℃ of shape memory transition temperatures when being lower than 10 ℃ of shape memory transition temperatures is than being 50-400.
The present invention comprises the solid content of water-based shape memory polyurethane composition of described shape memory polyurethane between 5%-50% (weight).Said composition preferably do not contain surpass 30% (weight) can be miscible with water organic solvent, for example methylformamide, acetone etc. more preferably do not contain any organic solvent.
The preparation method of shape memory polyurethane of the present invention comprises following reactions steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated;
B) in reaction process, add the chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) make products therefrom homodisperse in water in the step d) by under high-speed stirring, adding deionized water, preferably use 5 ℃ of-80 ℃ of deionized waters.
This method adopts the performed polymer synthesis method to prepare shape memory polyurethane, and at first, vulcabond and polyvalent alcohol are by certain mole proportioning A=[NCO]/[OH] reaction prepolymer.Then add chainextender.After the several hrs reaction, add end-capping reagent to react unreacted isocyano, add neutralizing agent and linking agent then, ionomeric polymer generates the negatively charged ion shape memory polyurethane.In the process of reaction, isocyanic acid (NCO) foundation group can react with carboxylic group, but the speed of its reaction is slower than the reaction of isocyanic acid (NCO) foundation group and oh group.Yet isocyanic acid under the certain reaction condition (NCO) foundation group reacts with carboxylic group, produces some amino chemical combination keys, forms cross-link bond in the molecule.In fact cross-link bond just produced in the stage of synthetic prepolymer.The aqueous dispersion of shape memory polyurethane can be prepared to obtain by the performed polymer of aforesaid urethane with comparalive ease.Generally include several steps: 1) use in the neutralizing agent and carboxylic group; 2) add protective material protection isocyano; 3) adding the Ionized performed polymer of water-dispersion, 4) prepolymer of chain extension adds the water that entry or adding contain polyamine (functionality is at 2.2-4) under condition of stirring.This several steps can once be finished.
Comprise excessive relatively vulcabond at the employed reactant reaction raw material of the preparation method of described shape memory polyurethane; oligomeric polyols; chainextender; end-capping reagent; linking agent; neutralizing agent and protective material can also add a spot of catalyzer such as dibutyltin dilaurate etc. in case of necessity in reaction process.
The molecular formula general formula that can be used for vulcabond of the present invention is: OCN-R-NCO, R represents one or two phenyl ring or only contains a plurality of methylene radical and cycloaliphatic ring, include, but not limited to aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and composition thereof.The object lesson of suitable aliphatic diisocyanate comprise isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate.The object lesson of suitable aromatic isocyanate comprises 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate.
What can be used for hydroxyl oligopolymer of the present invention includes, but not limited to polyester polyol, polyether glycol, polycarbonate, polycaprolactone and composition thereof.The object lesson of suitable hydroxyl oligopolymer comprises: polyvalent alcohols such as polypropylene glycol or polyoxytrimethylene ether glycol, polytetramethylene glycol, polytetramethylene glycol, polyvinyl alcohol, polycaprolactone (glycol), poly bisphenol.
The ratio of described vulcabond and hydroxyl oligopolymer is generally 1.1-2.5.
Can be used for the general molecular formula that contains the chainextender of active hydrogen group of the present invention is: OH-R "-OH; R " represent 2-12 methylene radical, 1-2 six-ring or contain the carboxylate radical of 1-2, comprise, but be not limited to, carboxylic glycol, 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane.Preferred chainextender is a dimethylol propionic acid.
Can be used for neutralizing agent of the present invention and be selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, comprise trolamine, triethylamine, sodium hydroxide, potassium hydroxide and their mixture.
Can be used for linking agent of the present invention and include, but not limited to water miscible small molecules polyvalent alcohol and polyhydric alcohol amine.The object lesson of suitable linking agent comprises glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine.
Can be used for end-capping reagent of the present invention and include, but not limited to weakly acidic salt or other organic end-capping reagent.The object lesson of suitable end-capping reagent comprises Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
In neutralization reaction, the consumption of neutralizing agent want can in and the carboxylic group that contained in the performed polymer.The mol ratio of institute's carboxyl group and neutralizing agent is at 1:(0.5-1.2 in the urethane).
The preparation method of a kind of shape memory fabrics provided by the present invention comprises and uses the finishing composition comprise water-based shape memory polyurethane composition of the present invention that substrate fabric is put in order.Finishing composition can adopt following prescription: the urethane of 4-10% weight; The softening agent of 1-3% weight; Permeate agent with 1-3% weight.Adjustment method can adopt following steps to carry out:
A) fabric padding finishing agent (two soak two rolls mangle expression 100%~150%);
B) oven dry (80~90 ℃, 1~3 minute); With
C) bake and bank up with earth (140~170 ℃, 1~3 minute).
The preparation method of another kind of shape memory fabrics provided by the present invention comprises and uses the coating-forming agent comprise water-based shape memory polyurethane composition of the present invention that substrate fabric is applied.Coating procedure can carry out with blade coating, roller coating or impregnation method.Solid content is for being generally 10-60% (weight) in the used coating agent, and preferred solid content is 20-50% (weight), to guarantee that the coating amount is generally 10-200g/m to do weightening finish on fabric 2, be preferably 20-100g/m 2
In described method, further comprise and handle coated fabric with flocculation agent.The available flocculation agent comprises in the present invention, but be not limited to, organic or inorganic acid such as metal-salt such as aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, sylvite and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, and the mixture that constitutes of these materials.In use, the concentration of described flocculation agent is generally 0.5-40% by weight, is preferably 1-20%.Coated substrate fabric treatment time in flocculation agent was generally 10 seconds to 10 minutes, was preferably 1 to 5 minute.
The substrate fabric that can be used for shape memory fabrics preparation method of the present invention includes, but not limited to nonwoven fabric and textile fabric, is preferably natural fiber, regenerated fiber or synthon or mixed fibre.
Shape memory fabrics provided by the present invention is characterized in that, contains shape memory polyurethane of the present invention through arrangement or coating on it.End capped isocyano can baked and banked up with earth deblocking under the temperature on the wherein said water-based shape memory polyurethane, self takes place crosslinked or reacts with reactive group on the fabric fibre, has strengthened shape memory function and the water tolerance and the chemical-resistant of fabric.
Below in conjunction with specific embodiment the present invention is further detailed.
Embodiment
The preparation of water-based shape memory polyurethane
In a four-hole boiling flask of being furnished with the protection of mechanical stirrer, drying nitrogen, prolong, add low poly-dihydric alcohol, vulcabond, a spot of solvent dimethyl formamide or do not need solubilizing agent.Under nitrogen protection, be heated to 80 ℃-90 ℃ and also reacted with this understanding 2-3 hour, obtain the performed polymer of urethane.Add chainextender then and comprise that the chainextender that contains carboxyl also continues reaction 2 hours, adds a certain amount of end-capping reagent again to react remaining isocyano.
In above-mentioned reaction mixture, add neutralizing agent and linking agent, the quantity of neutralizing agent in theory can be fully in chainextender in carboxylic group.Neutralizing agent reacted 10-20 minute with reaction mixture about 50 ℃.The hypothermic response thing adds protective material for 0 ℃-5 ℃ to room temperature, under the effect of high speed agitator (1000-2000rpm), adds entry lentamente in polymkeric substance.For dispersed polymeres better, can add a spot of acetone sometimes.The content of final polymkeric substance is at 20%-60%.The solvent that contains in the solution is removed by underpressure distillation.
Embodiment 1
Polycaprolactone (the PLACCEL240 that adds 120g, DacielChemicalIndustries, LTD.) (molecular weight 4000, dry), with the diphenylmethanediisocyanate of 30g in 500 milliliters, band mechanical stirring, be connected in the four-hole glass flask of nitrogen port.Feed drying nitrogen, mechanical stirring remains under 80 ℃~90 ℃ temperature and reacted 3 hours.Add 1 of 2.7g dimethylol propionic acid and 4.5g then successively, the 4-butyleneglycol continues reaction 2 hours as under the condition of chainextender between keeping 80 ℃~90 ℃.Can add a spot of dimethyl formamide in this reaction process.Then reduce the temperature to 50 ℃ of reactant, the triethylamine that adds 2.2g is with the carboxyl in the neutralization reactant.At last add 250 milliliters of deionized waters that contain 4.2g sulfurous hydracid sodium down, obtain solid content and be 25% water white water-based shape memory polyurethane in the high-speed stirring (1000rpm) of agitator.In the present embodiment, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: the mol ratio=120:30:70:22:40 of end-capping reagent.The thin film shape memory transition temperature that makes through present embodiment is 45 ℃.Shape-memory properties test: the film that obtains with this polyurethane preparation stretches one times through 55 ℃, is cooled to 35 ℃ of typings then, returns to original shape in 45 ℃ water-bath fully.
Embodiment 2
The polypropylene glycol (molecular weight 2000, dry) that adds 48g is with the diphenylmethanediisocyanate to 500 of 20g milliliter, band mechanical stirring, be connected in the four-hole glass flask of nitrogen port.Feed exsiccant nitrogen, under the effect of agitator, keep 80 ℃~90 ℃ reactions of temperature 3 hours.Add 1 of 3.2g dimethylol propionic acid and 1.5g then successively, the 4-butyleneglycol continues reaction 2 hours as under the condition of chainextender between keeping 80 ℃~90 ℃, adds the 2.8g Diacetylmonoxime then and continues reaction 2 hours.Can add a spot of dimethyl formamide in this reaction process.Then reduce the temperature to 50 ℃ of reactant, add the carboxyl in the diethanolamine neutralization reactant of 2.6g.High-speed stirring (1000rpm) at agitator adds 100 milliliters of deionized waters down at last, and obtaining solid content is the water-based shape memory polyurethane of 40% (weight).In the present embodiment, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: the mol ratio=80:24:40:26:32 of linking agent.The thin film shape memory transition temperature that makes through present embodiment is 10 ℃.Shape-memory properties test: the film that obtains with this polyurethane preparation stretches one times through 20 ℃, is cooled to 0 ℃ of typing then, returns to original shape in 10 ℃ water-bath fully.
The preparation of shape-memory-fabric finishing liquid
Embodiment 1 resulting water-based shape memory polyurethane is diluted with deionized water, and interpolation softening agent and permeate agent, to be mixed with solid content 6%, softening agent (SG-6, Hai'an, Jiangsu petroleum chemical plant) 2%, the shape-memory-fabric finishing liquid of permeate agent (JFC, Hai'an, Jiangsu petroleum chemical plant) 2%.
The preparation of shape memory fabrics
Embodiment 3
To treat finish fabric (42/43 "; 30s * 30s, 68 * 68,100% cotton; bleach) be immersed in the water-based shape memory polyurethane dressing liquid of above-mentioned preparation that (solid content 6%; softening agent 2%, permeate agent 2%, two soaks two and rolls; the mangle expression weight ratio is 100%; preliminary drying 3 minutes in 85 ℃ of baking ovens then, bakes and banks up with earth 2 minutes at 150 ℃ again, is cooled to room temperature and promptly gets shape memory fabrics.
Embodiment 4
With pretreating fabrics (42/43 "; 30s * 30s; 68 * 68; 100% cotton; bleach) with blade coating; roller coating or impregnation method are coated the water-based shape memory polyurethane coating-forming agent (solid content 40 weight %) as embodiment 2 preparation equably, when coating is not dried, immerse the cohesion fill the Tai-Ace S 150 flocculation agent aqueous solution and carry out wet method film forming (coagulation liquid concentration 2% in bathing 40 ℃, 2 minutes), to be coated on 80 ℃ of oven dry then, in 0~60 ℃ water, soaked 5~30 minutes then, go up residual flocculation agent and other solvend to remove coating, promptly get film thickness and be 0.5 millimeter shape memory fabrics finished product.
The test of shape memory fabrics (sample adopts the product of the foregoing description 3,4 preparations)
Table 1 shape memory fabrics is at the crease resistance of room temperature
Embodiment 3 Embodiment 4
Rate of body weight gain (%) 6.2 5.8
Dry creasing angle (warp-wise and broadwise) 280 degree 270 degree
Ultimate strength retention rate (%) 96 95
The DP grade 4.3 4.2
Annotate: the dry creasing angle of untreated fabric is 210 degree, adopts the crease recovery instrument of AATCC 66-1996 standard and DAIEI KAGAKU SEIKI LTD. to measure wrinkle recovery angle, adopts Instron 4411 apparatus measures strength retentions.
As can be seen from Table 1, shape memory fabrics has good crease resistance and powerful retention property in room temperature.
The crease resistance of table 2 shape memory fabrics in high temperature
Original Embodiment 3 Embodiment 4
Rate of body weight gain (%) -- 6.2 5.8
Folding line keeps grade (50 ℃ of hot water) 1.3 3.9 3.8
Fabric spreading (50 ℃ of hot water) 2.5 4.2 4
Folding line keeps grade (70 ℃ of warm airs) 1.2 3.9 3.8
Fabric spreading (70 ℃ of warm airs) 2.3 4.1 4
Ultimate strength retention rate (%) 100 102 98
Annotate: folding line keeps grade and fabric spreading utilization U.S. AATCC-88C and AATCC-124 judgement criteria, and the fabric folding line is in advance prior to pressing folding line three minutes with flatiron in 140 ℃ of high temperature.
As can be seen from Table 2, the folding line of shape memory fabrics when high temperature well kept.
Protection scope of the present invention is not limited to the foregoing description, and should be as the criterion with the content that limits in the claim.Those skilled in the art can do various changes with enforcement the present invention to specific embodiments of the invention or parameter etc., and needn't pay performing creative labour according to of the present invention open.Therefore, protection scope of the present invention should be understood to comprise the variation and the change of these routines.

Claims (49)

1. urethane, its weight-average molecular weight is characterized in that between 10000 to 100000, and this urethane is that the prepolymer with following component reaction preparation continues to react resulting polymkeric substance in water:
1) vulcabond;
2) hydroxyl oligopolymer, wherein said hydroxyl oligopolymer is selected from polyester polyol, polyether glycol, polycarbonate and composition thereof;
3) contain active hydrogen group chainextender and carboxylic chainextender;
4) contain the neutralizing agent of basic group;
5) end-capping reagent;
6) linking agent, and
7) Ren Xuan catalyzer,
It is characterized in that described urethane is with the isocyano of the different molal quantity ratios of NCO/OH=0.8~1.6 and hydroxy-end capped, wherein, and described component molar ratio is, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: linking agent: catalyzer=0.8~1.6:0.2~0.8:0.4~1:0.2~0.6:0~1.2:0~0.4:0~0.02, described urethane has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.
2. urethane as claimed in claim 1 is characterized in that, the molar ratio of described vulcabond and hydroxyl oligopolymer is 1.1-2.5.
3. urethane as claimed in claim 1 is characterized in that described vulcabond is selected from aliphatic diisocyanate, aromatic diisocyanate and composition thereof.
4. urethane as claimed in claim 3 is characterized in that, described aliphatic diisocyanate be selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate.
5. urethane as claimed in claim 3 is characterized in that described aromatic diisocyanate is selected from 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate.
6. urethane as claimed in claim 1 is characterized in that, the described chainextender that contains active hydrogen group is selected from 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane.
7. urethane as claimed in claim 1 is characterized in that, described carboxylic chainextender is selected from dimethylol propionic acid.
8. urethane as claimed in claim 1 is characterized in that described neutralizing agent is selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, and in described neutralizing agent and the urethane ratio of contained carboxyl at 1:0.5 between the 1:1.2.
9. urethane as claimed in claim 1 is characterized in that, described linking agent is selected from water miscible small molecules polyvalent alcohol and polyhydric alcohol amine.
10. urethane as claimed in claim 9 is characterized in that described linking agent is selected from glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine.
11. urethane as claimed in claim 1 is characterized in that, described end-capping reagent is selected from Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
12. a polyurethane composition, it comprises among the claim 1-11 each urethane and water, and the solid content of described composition is 5 weight %-50 weight %.
13. polyurethane composition as claimed in claim 12 is characterized in that, do not contain surpass 30 weight % can be miscible with water organic solvent.
14. polyurethane composition as claimed in claim 12 is characterized in that, does not contain any organic solvent.
15. the preparation method as each described urethane among the claim 1-11 comprises the steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated, wherein said hydroxyl oligopolymer is selected from polyester polyol, polyether glycol, polycarbonate and composition thereof;
B) in reaction process, add chainextender and the carboxylic chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) gained prepolymer in the step d) is scattered in the water, makes it to continue reaction.
16. preparation method as claimed in claim 15 is characterized in that, the ratio of described vulcabond and hydroxyl oligopolymer is 1.1-2.5.
17. preparation method as claimed in claim 15 is characterized in that, described vulcabond is selected from aliphatic isocyanates, aromatic isocyanate and composition thereof.
18. preparation method as claimed in claim 17 is characterized in that, described aliphatic diisocyanate be selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate.
19. preparation method as claimed in claim 17 is characterized in that, described aromatic diisocyanate is selected from 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate.
20. preparation method as claimed in claim 15 is characterized in that, the described chainextender that contains active hydrogen group is selected from 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane.
21. preparation method as claimed in claim 15 is characterized in that, the described chainextender that contains carboxyl is a dimethylol propionic acid.
22. preparation method as claimed in claim 15 is characterized in that, described neutralizing agent is selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, and in described neutralizing agent and the urethane ratio of contained carboxyl at 1:0.5 between the 1:1.2.
23. preparation method as claimed in claim 15 is characterized in that, the water that uses in the step e) is deionized water, and the temperature of this deionized water is at 5-80 ℃.
24. preparation method as claimed in claim 15 is characterized in that, described linking agent is selected from water miscible small molecules polyvalent alcohol and polyhydric alcohol amine.
25. preparation method as claimed in claim 24 is characterized in that, described linking agent is selected from glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine.
26. preparation method as claimed in claim 15 is characterized in that, described end-capping reagent is selected from Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
27. the preparation method of a shape memory fabrics comprises using to comprise as the finishing composition of each urethane among the claim 1-11 substrate fabric is put in order.
28. preparation method as claimed in claim 27 is characterized in that, described adjustment method comprises the steps: a) to pad substrate fabric with finishing composition; B) oven dry; And c) bakes and banks up with earth.
29. preparation method as claimed in claim 27 is characterized in that, described adjustment method comprises the steps: a) to pad substrate fabric with finishing composition, and two soak two rolls mangle expression 100%~150%; B) 80~90 ℃ of oven dry 1~3 minute; And c) baked and banked up with earth 1~3 minute at 140~170 ℃.
30., it is characterized in that described finishing composition comprises following composition: the urethane of 4-10% weight part as each described preparation method among the claim 27-29; The softening agent of 1-3% weight part; Permeate agent with the 1-3% weight part.
31. as each described preparation method among the claim 27-29, described substrate fabric is textile fibres or non-woven fibre.
32., it is characterized in that described fiber is the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers as each described preparation method among the claim 27-29.
33. the preparation method of a shape memory fabrics comprises and uses the coating-forming agent that contains as each described urethane among the claim 1-11 that substrate fabric is applied.
34. preparation method as claimed in claim 33 wherein also comprises with flocculation agent and handles the substrate fabric that has applied.
35. preparation method as claimed in claim 33 wherein carries out coated with blade coating, roller coating or impregnation method.
36. preparation method as claimed in claim 33, wherein solid content is 10-60 weight % in the used coating agent.
37. preparation method as claimed in claim 33, wherein solid content is 20-50 weight % in the used coating agent.
38. preparation method as claimed in claim 33 is wherein to cause on the fabric coating amount to count 10-200g/m to do weightening finish 2The agent of amount applying coating.
39. preparation method as claimed in claim 33 is wherein to cause on the fabric coating amount to count 20-100g/m to do weightening finish 2The agent of amount applying coating.
40. preparation method as claimed in claim 34, wherein used flocculation agent is the metal-salt that is selected from aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, sylvite, perhaps be selected from the organic or inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, perhaps be selected from the mixture that described material constitutes.
41. preparation method as claimed in claim 34, the concentration of wherein said flocculation agent are 0.5-40% by weight.
42. preparation method as claimed in claim 34, the concentration of wherein said flocculation agent are 1-20% by weight.
43. preparation method as claimed in claim 34, the substrate fabric that has wherein applied treatment time in flocculation agent is 10 seconds to 10 minutes.
44. preparation method as claimed in claim 34, the substrate fabric that has wherein applied treatment time in flocculation agent is 1 to 5 minute.
45. preparation method as claimed in claim 33 is characterized in that, described substrate fabric is textile fibres or non-woven fibre.
46. preparation method as claimed in claim 33 is characterized in that, described fiber is the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers.
47. a shape memory fabrics is characterized in that, it comprises among substrate fabric and the claim 1-11 each urethane, on the wherein said substrate fabric through arrangement or apply and contain described urethane.
48. the described fabric of claim 47 is characterized in that, described substrate fabric is textile fibres or non-woven fibre.
49. fabric as claimed in claim 47 is characterized in that, described fiber is the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers.
CNB2004100025522A 2004-01-30 2004-01-30 Polyurethane with shape memory property, composition containing it and shape memory fabric prepared therefrom Expired - Lifetime CN100523038C (en)

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