CN103351456B - Wet method polyurethane resin for clothing leather, and preparation method thereof - Google Patents
Wet method polyurethane resin for clothing leather, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a wet method polyurethane resin for clothing leather, and a preparation method thereof. The raw material formula of the polyurethane resin comprises 5-15% of ester ether copolymer polyol, 5-15% of diisocyanate, 2-5% of a micro-molecular alcohol chain extender, 0.01-0.1% of a catalyst, 10-20% of a polyurethane intermediate having a viscosity of 120-180Pa.s/25DEG C, 0.05-2% of an aid, and 50-70% of a solvent; and the ester ether copolymer polyol is prepared through reacting binary acid or acid anhydride with polyol, has a number-average molecular weight of 1200-10000 and a hydroxyl value of 10-100mgKOH/g. The polyurethane resin has an excellent hydrolysis resistance and a good hand feeling, and satisfies people's pursuits of real leather feelings comprising the comfortableness, the flesh feeling, the softness and the like of the clothing leather.
Description
Technical field
The present invention relates to wet polyurethane resin and preparation method thereof for a kind of clothing leather.
Background technology
Generally, use for synthetic leather urethane resin is to adopt polyvalent alcohol and various vulcabond in DMF equal solvent, by condensation polymerization, to form performed polymer under catalyzer existence, then by small molecule alcohol or amine through chain extending reaction and add various auxiliary agents and form.Wherein said polyvalent alcohol is of a great variety, has polyester type, polyether-type etc.; Described vulcabond can be used tolylene diisocyanate (TDI), 4,4-ditane-vulcabond (MDI) etc.; Conventional solvent has DMF, toluene, dimethylbenzene, butanone organic solvent etc.; Conventional small molecule alcohol chainextender comprises ethylene glycol, Diethylene Glycol, Triethylene glycol, tetraethylene-glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, neopentyl glycol etc.; Described catalyzer comprises the conventional catalyzer such as organotin, organo-bismuth; And auxiliary agent is mainly the silicone oil such as various organosilicons of adjusting foam structure or improving feel.
In recent years, in order to meet the ever-increasing requirement in performance of Synthetic Leather goods, people have done a large amount of research and development in this field.Various documents and patent are in succession reported and are disclosed people at urethane resin and in the scientific research achievement in synthetic leather field.Yin Ning etc. are (< < polymer material science and engineering > > in the research > > of < < polyether ester segmented copolymer raising Hydrolysis Stability of Polyurethane Elastomers, 2007, the 23rd 4 phases of volume) introduced and adopted bimetallic catalyst to take the poly(propylene oxide) that hexanodioic acid series polyester polyol is initiator, the ester ether block polymer of propylene oxide has also been set forth its performance aspect hydrolysis and in the application in elastomerics field.Patent CN101381448 discloses a kind of polyurethane resin for water proof and breathable clothing leather product and has had high thoroughly wet high water pressure resistance, and performance reaches external product level, but it lays particular emphasis on the ventilation property of leather goods.Patent CN101050265A discloses a kind of wet mild polyurethane resin in use for synthetic leather and preparation method thereof, this invention is for clothes or case and bag, frosted fine hair sense is afterwards strong, and color developing is good, does not provide the advantage of this invention in the performances such as hydrolysis, stripping strength.Patent CN1816579A and patent CN101851325A disclose respectively the low temperature resistant polyurethane synthetic leather resin of heat-resisting hydrolysis and polyester type hydrolysis high-peel-strength polyurethane resin and preparation method thereof for wet-method synthetic leather, but raw materials used cost is expensive, be unfavorable for promoting.So can find out that the urethane resin over-all properties that now sell in current disclosed patent and market has much room for improvement.In addition, in synthetic leather product, wet method process hides product restricts it because pliability, feel, kishke feel are undesirable and further promotes.They or lay particular emphasis on ventilation property or lay particular emphasis on hydrolysis or lay particular emphasis on height and peel off or lay particular emphasis on low temperature resistant, and ignored people's pursuit to kishke feels such as comfortableness, voluptuousness, softnesses in polyurethane clothing leather.Meanwhile, Cost Problems also becomes the factor that restriction this area product application is promoted gradually.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that comfortableness, feel and flexibility are poor and cost is higher of wet polyurethane for the clothing leather of prior art, and a kind of improved clothing leather wet polyurethane resin is provided.
The present invention also will provide the preparation method of a kind of clothing leather with wet polyurethane resin simultaneously, the method cost is lower, and gained clothing leather has excellent anti-hydrolytic performance with wet polyurethane resin, soft handle, meets the pursuit of people to kishke feels such as the comfortableness of clothing leather, voluptuousness, softnesses.
For solving the problems of the technologies described above, a kind of technical scheme that the present invention takes is:
A kind of clothing leather wet polyurethane resin, in weight content, clothing leather is as follows with the composition of raw materials of wet polyurethane resin: ester ether copolymer polyvalent alcohol 5%～15%, vulcabond 5%～15%, small molecular alcohol chainextender 2%～5%, catalyzer 0.01%～0.1%, urethane intermediate 10%～20%, auxiliary agent 0.05%～2% and solvent 50%～70%;
In weight content, the composition of raw materials of described urethane intermediate is as follows: ester ether copolymer polyvalent alcohol 10%～20%, vulcabond 3%～15%, small molecular alcohol chainextender 1%～3%, catalyzer 0.01%～0.1%, auxiliary agent 0.05%～2% and solvent 60%～85%, described urethane intermediate reacts gained by its raw material at 50 ℃～90 ℃, and viscosity is 120～180Pa.s/25 ℃;
Described ester ether copolymer polyvalent alcohol is made by diprotic acid or acid anhydrides and polyol reaction, its number-average molecular weight is 1200～10000, hydroxyl value is 10～100mgKOH/g, wherein diprotic acid is comprised of by weight 2～8:1 aromatic acid or its acid anhydrides and aliphatic dibasic acid, and the polyether glycol that described polyvalent alcohol is 100～450 by number-average molecular weight and small molecules dibasic alcohol by weight 2～15:1 form.
Preferably, described aromatic acid or its acid anhydrides are one or more the combination being selected from phthalic acid, Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid.Described aliphatic dibasic acid is succinic acid or hexanodioic acid or the combination of the two.
According to the present invention, the polyether glycol that described polyether glycol can make through polyaddition reaction for alcohols or amine initiator and oxyethane, propylene oxide, tetrahydrofuran (THF) or their combination.For example, polyether glycol can be polyethylene oxide glycol, polypropylene oxide glycol or polytetrahydrofuran diol, or polyether glycol is two kinds of glycol that above combination ring-opening polymerizations form in oxyethane, propylene oxide, tetrahydrofuran (THF).The number-average molecular weight of polyether glycol is preferably 150～350.
According to the present invention, described small molecular alcohol chainextender, described small molecules dibasic alcohol can be the conventional dibasic alcohol in this area, for example they can be independently for being selected from one or more the combination in ethylene glycol, Diethylene Glycol, Triethylene glycol, tetraethylene-glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol and neopentyl glycol.
Preferably, the number-average molecular weight of described ester ether copolymer polyvalent alcohol is 3500～9000, and hydroxyl value is 12～32mgKOH/g.
According to the present invention, described auxiliary agent is the various auxiliary agents that those skilled in the art are familiar with, for example can be for being selected from one or more the combination in organic silicon modified by polyether class softening agent, abscess conditioning agent, release agent and oxidation inhibitor.Preferably, described auxiliary agent is the combination of organic silicon modified by polyether class softening agent, abscess conditioning agent, release agent and oxidation inhibitor.
According to the present invention, described catalyzer, vulcabond, solvent etc. are conventional those in this area, such as catalyzer, can be organic tin such as stannous octoate, organo-bismuth class catalyzer etc.; Vulcabond has for example tolylene diisocyanate (TDI), 4,4-'-diphenylmethane diisocyanate (MDI) etc.; Solvent has DMF, toluene, butanone etc.
According to the present invention: described ether-ether polyol can adopt nitrogen-decompression well-known to those skilled in the art (normal pressure)-autoclave-batch production technique to prepare.
The another technical scheme that the present invention takes is: the preparation method of wet polyurethane resin for a kind of above-mentioned clothing leather, it comprises the steps:
(1), prepare urethane intermediate: by formula, each raw material is joined in the reactor of nitrogen protection, be warming up to 50 ℃～90 ℃, after reaction 4～16h, lower the temperature, test reaction thing viscosity is 120～180Pa.s/25 ℃, standby;
(2), prepare clothing leather wet polyurethane resin: by formula, each raw material except urethane intermediate is joined in the reactor of nitrogen protection; be warming up to 50 ℃～90 ℃; after reaction 4～16h, lower the temperature; test reaction thing viscosity is 200～290Pa.s/25 ℃; the urethane intermediate that adds step (1) to prepare; stir, packing, obtains described clothing leather wet polyurethane resin.
According to further scheme of the present invention: described method also comprises the step of preparing ester ether copolymer polyvalent alcohol; specific as follows: described diprotic acid or acid anhydrides and polyvalent alcohol, catalyzer are joined in the reactor that stirring, temperature control are housed of nitrogen protection; esterification and transesterification reaction are carried out in intensification, obtain.In actually operating, can control as required the vacuum tightness of reaction system, after the qualifieds such as product viscosity, acid number, hydroxyl value, moisture content, cooling packing.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention has designed a kind of ester ether copolymer polyvalent alcohol with specific molecular structure and molecular weight, this certain esters ether copolymer polyvalent alcohol is incorporated in polyurethane molecular structure, makes urethane resin not only keep intensity, the fastness of polyester urethane resin but also kept anti-hydrolytic performance, the low temperature kindliness of polyether(poly)urethane resin.The aromatic micromolecule materials such as the terephthalic acid adopting in molecule have strengthened thermotolerance and the stripping strength of product.The polyether glycol of the larger molecular weight simultaneously adopting makes wet-method synthetic leather product prepared by urethane resin have goodish kindliness as the soft segment of synthesis of polyurethane resin.Another feature of the present invention is first to synthesize the urethane resin intermediate of a kind of certain viscosity and solid content, then this intermediate is added in final urethane resin.This technique is conducive to make wet polyurethane synthetic leather product of the present invention to have better pliability, wet and slippery sense, plentiful feel, and kishke feel is stronger.So clothing leather provided by the present invention is taken into account with wet polyurethane resin, the desired hydrolysis in this area, height are peeled off, the super performance requriements such as soft, have again good kishke feel.And raw material supply is comparatively sufficient, cheap, has larger market potential.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.
Embodiment 1
This example provides a kind of ester ether copolymer polyvalent alcohol, and its composition of raw materials is referring to table 1:
Table 1
The preparation method of ester ether copolymer polyvalent alcohol is as follows: various raw materials in table 1 are joined in the four-hole round-bottomed flask that mechanical stirring, nitrogen, temperature controller, condensing reflux equipment are housed, be warming up to gradually 220 ℃ of constant temperature 15h after test products acid number at 0.45mgKOH/g, hydroxyl value be after 15.5mgKOH/g, lower the temperature standby.
Embodiment 2
This example provides a kind of ester ether copolymer polyvalent alcohol, and its composition of raw materials is referring to table 2:
Table 2
The preparation method of ester ether copolymer polyvalent alcohol is as follows: various raw materials in table are joined in the four-hole round-bottomed flask that mechanical stirring, nitrogen, temperature controller, condensing reflux equipment are housed, be warming up to gradually 225 ℃ of constant temperature 18h after test products acid number at 0.35mgKOH/g, hydroxyl value be after 18.5mgKOH/g, lower the temperature standby.
Embodiment 3
This example provides a kind of ester ether copolymer polyvalent alcohol, and its composition of raw materials is referring to table 3:
The preparation method of ester ether copolymer polyvalent alcohol is as follows: various raw materials in table are joined in the four-hole round-bottomed flask that mechanical stirring, nitrogen, temperature controller, condensing reflux equipment are housed, be warming up to gradually 230 ℃ of constant temperature 17h after test products acid number at 0.39mgKOH/g, hydroxyl value be after 14.8mgKOH/g, lower the temperature standby.
Embodiment 4
This example provides a kind of urethane intermediate, and its composition of raw materials is referring to table 4, and wherein ester ether copolymer polyvalent alcohol used derives from embodiment 1.
Table 4
The preparation method of urethane intermediate is as follows: each raw material in table is joined after being warming up to 70-90 ℃ of reaction 10-12h in the reactor of nitrogen protection and is lowered the temperature, test reaction product viscosity be 180Pas/25 ℃, solid content 26.4%, standby.
Embodiment 5
This example provides a kind of urethane intermediate, and its composition of raw materials is referring to table 5, and wherein ester ether copolymer polyvalent alcohol used derives from embodiment 2.
Table 5
The preparation method of urethane intermediate is as follows: each raw material in table is joined after being warming up to 70-90 ℃ of reaction 10-12h in the reactor of nitrogen protection and is lowered the temperature, test reaction product viscosity be 170Pas/25 ℃, solid content 25.2%, standby.
Embodiment 6
This example provides a kind of urethane intermediate, and its composition of raw materials is referring to table 6, and wherein ester ether copolymer polyvalent alcohol used derives from embodiment 3.
Table 6
The preparation method of urethane intermediate is as follows: each raw material in table is joined after being warming up to 70-90 ℃ of reaction 15-16h in the reactor of nitrogen protection and is lowered the temperature, test reaction product viscosity be 130Pas/25 ℃, solid content 18.4%, standby.
Embodiment 7
This example provides a kind of clothing leather wet polyurethane resin, and its composition of raw materials is referring to table 7, and wherein ester ether copolymer polyvalent alcohol used is from embodiment 1, and urethane intermediate is from embodiment 4.
Table 7
| Material name | Usage quantity (g) |
| DMF | 1200 |
| Ester ether copolymer polyvalent alcohol | 230 |
| Hexylene glycol | 82 |
| MDI | 185 |
| Oxidation inhibitor I-1010 | 0.6 |
| Organo-bismuth class catalyzer | 0.5 |
| Organic silicon modified by polyether class softening agent | 2 |
| Urethane intermediate | 200 |
The preparation method of urethane resin is as follows: each raw material except urethane intermediate in table is joined after being warming up to 70-90 ℃ of reaction 12-13h in the reactor of nitrogen protection and lower the temperature, in system, add urethane resin intermediate and stir.Test reaction product viscosity is that 230Pas/25 ℃, solid content are 29.4%.
Embodiment 8
This example provides a kind of clothing leather wet polyurethane resin, and its composition of raw materials is referring to table 8, and wherein ester ether copolymer polyvalent alcohol used is from embodiment 2, and urethane intermediate is from embodiment 5.
Table 8
| Material name | Usage quantity (g) |
| Toluene | 1010 |
| Ester ether copolymer polyvalent alcohol | 255 |
| Ethylene glycol | 35 |
| TDI | 110 |
| Oxidation inhibitor I-1010 | 0.6 |
| Organo-bismuth class catalyzer | 0.5 |
| Organic silicon modified by polyether class softening agent | 2 |
| Urethane intermediate | 300 |
The preparation method of urethane resin is as follows: each raw material outside urethane intermediate in table is joined after being warming up to 70-90 ℃ of reaction 12-13h in the reactor of nitrogen protection and lower the temperature.In system, add urethane resin intermediate and stir.Test reaction product viscosity is that 220Pas/25 ℃, solid content are 30.4%.
Embodiment 9
This example provides a kind of clothing leather wet polyurethane resin, and its composition of raw materials is referring to table 9, and wherein ester ether copolymer polyvalent alcohol used is from embodiment 3, and urethane intermediate is from embodiment 6.
Table 9
| Material name | Usage quantity (g) |
| DMF | 1680 |
| Ester ether copolymer polyvalent alcohol | 200 |
| Butyleneglycol | 84 |
| MDI | 245 |
| Oxidation inhibitor I-1010 | 0.6 |
| Organo-bismuth class catalyzer | 0.5 |
| Organic silicon modified by polyether class softening agent | 2 |
| Urethane intermediate | 300 |
The preparation method of urethane resin is as follows: each raw material outside urethane intermediate in table is joined after being warming up to 70-90 ℃ of reaction 12-13h in the reactor of nitrogen protection and lower the temperature.In system, add urethane resin intermediate and stir.Test reaction product viscosity is that 220Pas/25 ℃, solid content are 30.4%.
Comparative example 1
This example provides a kind of wet polyurethane resin, and its composition of raw materials is referring to table 10.
Table 10
| Material name | Usage quantity (g) |
| DMF | 1080 |
| PTMG2000 | 300 |
| Ethylene glycol | 25 |
| MDI | 140 |
| Oxidation inhibitor I-1010 | 0.6 |
| Organo-bismuth class catalyzer | 0.5 |
| Organic silicon modified by polyether class softening agent | 2 |
The preparation method of urethane resin is as follows: each raw material in table is joined after being warming up to 70-90 ℃ of reaction 10-12h in the reactor of nitrogen protection and is lowered the temperature, test reaction product viscosity be 220Pas/25 ℃, solid content 30.2%, standby.
Comparative example 2
This example provides a kind of wet polyurethane resin, and its composition of raw materials is referring to table 11.
Table 11
The preparation method of urethane resin is as follows: each raw material in table is joined after being warming up to 70-90 ℃ of reaction 10-12h in the reactor of nitrogen protection and is lowered the temperature, test reaction product viscosity be 240Pas/25 ℃, solid content 30.1%, standby.
Comparative example 3
This example provides a kind of wet polyurethane resin, and its composition of raw materials is referring to table 12.
Table 12
The preparation method of urethane resin is as follows: each raw material in table is joined after being warming up to 70-90 ℃ of reaction 10-12h in the reactor of nitrogen protection and is lowered the temperature, test reaction product viscosity be 170Pas/25 ℃, solid content 29.7%, standby.
Properties to the urethane resin of embodiment 7～9 and comparative example 1～3 is tested, specific as follows:
1, testing method
(1) spreading rod one-tenth flesh rate: be 1.00mm(± 0.01mm by coating clearance by the resin configuring (being comprised of 100 parts of resins, 25 parts of wood powders, DMF100 part)) is coated with the coating that 1mm is thick on sheet glass, then be placed in tank DMF is deviate from, in 100 ℃ of air dry ovens, after dry 30min, according to GB/T6672-2001 standard, carry out film thickness test and obtain L.Become flesh rate to be:
Become flesh rate=L/1*100%
In formula: L: slough film thickness after solvent, mm; 1: spreading rod thickness, mm;
(2) anti-hydrolytic performance peel load is measured:
Hydrolysis test condition: the stripping strength of 5%NaOH solution soaking test sample;
Peel strength test: be 1.40mm(± 0.01mm by coating clearance by the resin configuring (consisting of 100 parts of resins, 35 parts of wood powders, DMF120 part)) spreading rod is evenly coating on sheet glass.Then be placed in certain density DMF tank and deviate from DMF wherein, bonding with hydrolysis type polyurethane tackiness agent after dry 30min in the air dry oven of 100 ℃ after DMF purifies, and then in air dry oven, be dried 30min.According to QB/T4197-2011 appendix A regulation, cut out sample, adopt the test puller system that meets GB/1040.3-2006 regulation to test according to 5.9 standards in GB/T8949-2008.
(3) 100% modulus, tensile strength, elongation at break test: according to QB/T4197-2011 standard, measure.
2, test result: referring to table 13.
Table 13
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a clothing leather wet polyurethane resin, it is characterized in that: in weight content, described clothing leather is as follows with the composition of raw materials of wet polyurethane resin: ester ether copolymer polyvalent alcohol 5%～15%, vulcabond 5%～15%, small molecular alcohol chainextender 2%～5%, catalyzer 0.01%～0.1%, urethane intermediate 10%～20%, auxiliary agent 0.05%～2% and solvent 50%～70%;
In weight content, the composition of raw materials of described urethane intermediate is as follows: ester ether copolymer polyvalent alcohol 10%～20%, vulcabond 3%～15%, small molecular alcohol chainextender 1%～3%, catalyzer 0.01%～0.1%, auxiliary agent 0.05%～2% and solvent 60%～85%, described urethane intermediate reacts gained by its raw material at 50 ℃～90 ℃, and viscosity is 120～180Pas/25 ℃;
Described ester ether copolymer polyvalent alcohol is made by diprotic acid or acid anhydrides and polyol reaction, its number-average molecular weight is 1000～10000, hydroxyl value is 10～100mgKOH/g, wherein diprotic acid is comprised of by weight 2～8:1 aromatic acid or its acid anhydrides and aliphatic dibasic acid, and the polyether glycol that described polyvalent alcohol is 100～450 by number-average molecular weight and small molecules dibasic alcohol by weight 2～15:1 form;
Described clothing leather makes as follows with wet polyurethane resin: by formula, each raw material except urethane intermediate is joined in the reactor of nitrogen protection; be warming up to 50 ℃～90 ℃; after reaction 4～16h, lower the temperature; test reaction thing viscosity is 200～290Pas/25 ℃; add urethane intermediate; stir, packing, obtains described clothing leather wet polyurethane resin.
2. clothing leather wet polyurethane resin according to claim 1, is characterized in that: described aromatic acid or its acid anhydrides are one or more the combination being selected from phthalic acid, Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid.
3. clothing leather wet polyurethane resin according to claim 1 and 2, is characterized in that: described aliphatic dibasic acid is succinic acid or hexanodioic acid or the combination of the two.
4. clothing leather wet polyurethane resin according to claim 1, it is characterized in that: described polyether glycol is polyethylene oxide glycol, polypropylene oxide glycol or polytetrahydrofuran diol, or described polyether glycol is two kinds of glycol that above combination ring-opening polymerizations form in oxyethane, propylene oxide, tetrahydrofuran (THF).
5. according to the clothing leather wet polyurethane resin described in claim 1 or 4, it is characterized in that: the number-average molecular weight of described polyether glycol is 150～350.
6. clothing leather wet polyurethane resin according to claim 1, is characterized in that: described small molecular alcohol chainextender, described small molecules dibasic alcohol are independently for being selected from one or more the combination in ethylene glycol, Diethylene Glycol, Triethylene glycol, tetraethylene-glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol and neopentyl glycol.
7. clothing leather wet polyurethane resin according to claim 1, is characterized in that: the number-average molecular weight of described ester ether copolymer polyvalent alcohol is 3500～9000, and hydroxyl value is 12～32mgKOH/g.
8. clothing leather wet polyurethane resin according to claim 1, is characterized in that: described auxiliary agent is one or more the combination being selected from organic silicon modified by polyether class softening agent, abscess conditioning agent, release agent and oxidation inhibitor.
9. a preparation method for the use of the clothing leather described in any one claim wet polyurethane resin in claim 1 to 8, is characterized in that: comprise the steps:
(1), prepare urethane intermediate: by formula, each raw material is joined in the reactor of nitrogen protection, be warming up to 50 ℃～90 ℃, after reaction 4～16h, lower the temperature, test reaction thing viscosity is 120～180Pas/25 ℃, standby;
(2), prepare clothing leather wet polyurethane resin: by formula, each raw material except urethane intermediate is joined in the reactor of nitrogen protection; be warming up to 50 ℃～90 ℃; after reaction 4～16h, lower the temperature; test reaction thing viscosity is 200～290Pas/25 ℃; the urethane intermediate that adds step (1) to prepare; stir, packing, obtains described clothing leather wet polyurethane resin.
10. preparation method according to claim 9; it is characterized in that: described method also comprises the step of preparing described ester ether copolymer polyvalent alcohol; specific as follows: described diprotic acid or acid anhydrides and polyvalent alcohol, catalyzer are joined in the reactor that stirring, temperature control are housed of nitrogen protection; esterification and transesterification reaction are carried out in intensification, obtain.
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| CN115010901A (en) * | 2022-06-17 | 2022-09-06 | 佳化化学科技发展（上海）有限公司 | Low-viscosity hydrolysis-resistant photocuring polyurethane resin and preparation method and application thereof |
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