CN103467696B - A kind of preparation method of soft high-elasticity embossing sofa leather wet-method polyurethane resin - Google Patents
A kind of preparation method of soft high-elasticity embossing sofa leather wet-method polyurethane resin Download PDFInfo
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- CN103467696B CN103467696B CN201310356394.XA CN201310356394A CN103467696B CN 103467696 B CN103467696 B CN 103467696B CN 201310356394 A CN201310356394 A CN 201310356394A CN 103467696 B CN103467696 B CN 103467696B
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Abstract
The preparation method that the invention discloses a kind of soft high-elasticity embossing sofa artificial leather Wet-type polyurethane resin, polyhydric alcohol and mixture thereof are first carried out suitable prepolymerization reaction by it, add the quantitative di-isocyanate reaction regular hour and control during pre-polymerization；Pre-polymerization adds little molecule dihydroxylic alcohols after terminating and diamine mixing carries out chain extending reaction；Finally add modifier, auxiliary agent；Final resin viscosity controls to terminate reaction in critical field.Soft high-elasticity embossing sofa artificial leather Wet-type polyurethane resin of the present invention, solves after existing ordinary soft low modulus wet polyurethane resin finished leather elastic in feel, the defect that before and after embossing, the aspect such as feel change exists.Using synthetic leather not only soft, plentiful, the good springiness that the polyurethane resin of the present invention is made, and can meet embossability, embossing pattern is clearly full, and feel change can be kept before and after embossing little.
Description
Technical field
The preparation method that the present invention relates to a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin, belongs to technical field of polymer materials.
Background technology
Owing to the natural resources of corium product is limited, price is high, it is impossible to meet the growing market demand.And Synthetic Leather products material wide material sources, low price, good processability, increasingly leveling off to the characteristic of natural leather, the life fully meeting people is pursued.Polyurethane resin application in synthetic leather is mainly reflected in multiple fields such as clothing, case and bag, footwear, furniture, automobile, the development speed of leather polyurethane resin is more and more faster in recent years, in the face of being gradually increased of the market demand, higher requirement is proposed leather polyurethane resin.Such as, sofa artificial leather, clothing leather, glove leather etc. do not require nothing more than soft, plentiful, good springiness, also want to meet embossability, and embossing pattern is clearly full, and feel change can be kept before and after embossing little.At present, market occurs many soft low modulus Wet-type polyurethane resins, but elastic in feel, embossability and before and after embossing the aspect such as feel change there is also a certain distance so that the leather goods produced are difficult to meet the growing market demand.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin, elastic in feel to solve after ordinary soft low modulus wet polyurethane resin finished leather, embossability and the defect that before and after embossing, the aspect such as feel change exists.
The reaction mechanism of the present invention is: in polyurethane resin building-up process, and soft section selects the flexible PEPA better, containing ehter bond, it is ensured that resin soft, has good embossability simultaneously；Hard section is added appropriate highly polar amine chain extender, improves the rigidity of the polarity of resin, elasticity and hard section, improve pass support force during resin finished leather, it is ensured that before and after embossing, feel change is less；Finally add modifier and auxiliary agent, improve hair engaging aperture performance and richness during resin finished leather.Thus, this resin not only has soft, plentiful, good springiness；Can also meeting embossability, embossing pattern is clearly full, and feel can be kept before and after embossing to change the characteristics such as little.
For achieving the above object, the technical method that the present invention adopts is as follows:
The preparation method of a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin, comprises the following steps:
(1) put into various PEPA and mixture thereof in a kettle., antioxidant I-1010, partial solvent DMF mix, quantitative di-isocyanate reaction is put into again after stirring 10-15 minute, the 90% of the reasonable stoichiometric of now quantitative diisocyanate, during pre-polymerization, solid content should control at 50-60%, still temperature control is at 70-80 DEG C, and the response time controlled at 60-80 minute；
(2) little molecule dihydroxylic alcohols that molecular weight is 62-200g/mol and diamine mixed chain extender are added after, under adding catalyst existent condition, with diisocyanate generation chain extending reaction, along with being continuously increased of system viscosity, being gradually added remaining solvent DMF, final viscosity controls 120-220Pa S/25 DEG C；
(3) reaction adds terminator methanol after terminating, and finally adds modifier and auxiliary agent, to improve the wet type processing characteristics of resin；
(4) cool to 60 DEG C and be carried out below rushing down material, metering packing.
Described PEPA and mixture thereof composed as follows: poly-adipic acid diglycol BDO esterdiol: number-average molecular weight is 3000 ± 300g/mol, accounts for the 70-100wt% of polyol blends；Poly-adipate glycol diglycol esterdiol: number-average molecular weight is 2000 ± 200g/mol, accounts for the 30-0wt% of polyol blends；Described PEPA and mixture thereof and little molecule dihydroxylic alcohols and diamine mixed chain extender mol ratio 1:1.5-2.5.
The 0.1-0.2% that consumption is system gross weight of described antioxidant I-1010；The consumption of described solvent DMF is the 69-71% of system gross weight.
Described diisocyanate is 4,4 '-methyl diphenylene diisocyanate.
Described molecular weight is the little molecule dihydroxylic alcohols of 62-200g/mol and diamine mixed chain extender is one or both in ethylene glycol, 1,4-butanediol, 1,6-HD, diphenylmethanediamiand；Wherein when dihydroxylic alcohols mixes use with diamine, its molar ratio is 7-12:1；The consumption of described dihydroxylic alcohols and diamine mixed chain extender accounts for the 1-2% of system gross weight.
Described catalyst is organo-bismuth class catalyst MB20, and consumption is the 0.1-1 ‰ of PEPA and compound by weight thereof；Described modifier is acetic acid butyl cellulose, and consumption is the 1-1.5% of system gross weight；Described auxiliary agent is one or both the mixture in softening agent, levelling agent, and consumption is the 2-3% of system gross weight.
Described PEPA and mixture, diisocyanate, little molecule dihydroxylic alcohols and diamine mixed chain extender, solvent DMF all require that moisture content is less than 500ppm.
Beneficial effects of the present invention:
The soft high-elasticity embossing sofa artificial leather Wet-type polyurethane resin that the present invention prepares, solves after existing ordinary soft low modulus wet polyurethane resin finished leather elastic in feel, embossability and the defect that before and after embossing, the aspect such as feel change exists.Using synthetic leather not only soft, plentiful, the good springiness that the soft high-elasticity embossing sofa artificial leather Wet-type polyurethane resin of the present invention is made, also want to meet embossability, embossing pattern is clearly full, and feel change can be kept before and after embossing little.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and effect and be easy to understand, below in conjunction with detailed description of the invention, the present invention is expanded on further.
Embodiment 1:
Material name weight (unit K g)
Poly-adipic acid diglycol 1,4-butanediol ester glycol 650
Poly-adipate glycol diglycol esterdiol 200
Ethylene glycol 34
4,4-diphenylmethanediamiand 12
4,4-methyl diphenylene diisocyanate 232
Antioxidant I-10107.0
Catalyst MB200.3
Softening agent 120
Acetic acid butyl cellulose 50
DMF3050
Wherein, poly-adipic acid diglycol BDO esterdiol is: the PEPA of number-average molecular weight 3000 ± 300g/mol,
Poly-adipate glycol diglycol esterdiol is: the PEPA of number-average molecular weight 2000 ± 200g/mol.
It is prepared according to the following steps:
(1) put into various polyester polyols alcohol mixture in a kettle., antioxidant I-1010, part DMF mix, quantitative MDI reaction is put into again after stirring 10-15 minute, the 90% of the reasonable stoichiometric of now quantitative MDI, during pre-polymerization, solid content should control at 50-60%, still temperature control, at 70-80 DEG C, is reacted about 60-80 minute；
(2) then add DMF to stir 10 minutes, put into ethylene glycol (EG) and 4,4-diphenylmethanediamiands (MDA) afterwards, stir and within 20 minutes, put into MDI reaction again, add catalyst MB20 after reacting 30 minutes and continue reaction；
(3) MDI continuation reaction being continuously increased along with system viscosity are progressively added in midway, are gradually added required solvent DMF.Final viscosity controls 120-220Pa S/25 DEG C, and still temperature control is between 70-80 DEG C；
(4) reaction adds terminator methanol after terminating, and finally adds softening agent, modifier again；
(5) cool to 60 DEG C and be carried out below rushing down material, metering packing.
Embodiment 2:
Material name weight (unit K g)
Poly-adipic acid diglycol 1,4-butanediol ester glycol 750
Poly-adipate glycol diglycol esterdiol 100
Ethylene glycol 35
4,4-diphenylmethanediamiand 10
4,4-methyl diphenylene diisocyanate 229
Antioxidant I-10107.0
Catalyst MB200.3
Softening agent 120
Acetic acid butyl cellulose 50
DMF3040
Wherein, poly-adipic acid diglycol BDO esterdiol is: the PEPA of number-average molecular weight 3000 ± 300g/mol,
Poly-adipate glycol diglycol esterdiol is: the PEPA of number-average molecular weight 2000 ± 200g/mol.
It is prepared according to the following steps:
(1) put into various polyester polyols alcohol mixture in a kettle., antioxidant I-1010, part DMF mix, quantitative MDI reaction is put into again after stirring 10-15 minute, the 90% of the reasonable stoichiometric of now quantitative MDI, during pre-polymerization, solid content should control at 50-60%, still temperature control, at 70-80 DEG C, is reacted about 60-80 minute；
(2) then add DMF to stir 10 minutes, put into ethylene glycol (EG) and 4,4-diphenylmethanediamiands (MDA) afterwards, stir and within 20 minutes, put into MDI reaction again, add catalyst MB20 after reacting 30 minutes and continue reaction；
(3) MDI continuation reaction being continuously increased along with system viscosity are progressively added in midway, are gradually added required solvent DMF.Final viscosity controls 120-220Pa S/25 DEG C, and still temperature control is between 70-80 DEG C.
(4) reaction adds terminator methanol after terminating, and finally adds softening agent, modifier again；
(5) cool to 60 DEG C and be carried out below rushing down material, metering packing.
Embodiment 3:
Material name weight (unit K g)
Poly-adipic acid diglycol 1,4-butanediol ester glycol 800
Poly-adipate glycol diglycol esterdiol 50
1,4-butanediol 48
4,4-diphenylmethanediamiand 14
4,4-methyl diphenylene diisocyanate 224
Antioxidant I-10107.0
Catalyst MB200.3
Softening agent 120
Acetic acid butyl cellulose 50
DMF3065
Wherein, poly-adipic acid diglycol BDO esterdiol is: the PEPA of number-average molecular weight 3000 ± 300g/mol,
Poly-adipate glycol diglycol esterdiol is: the PEPA of number-average molecular weight 2000 ± 200g/mol.
It is prepared according to the following steps:
(1) put into various polyester polyols alcohol mixture in a kettle., antioxidant I-1010, part DMF mix, quantitative MDI reaction is put into again after stirring 10-15 minute, the 90% of the reasonable stoichiometric of now quantitative MDI, during pre-polymerization, solid content should control at 50-60%, still temperature control, at 70-80 DEG C, is reacted about 60-80 minute；
(2) then add DMF to stir 10 minutes, put into BDO (BG) and 4,4-diphenylmethanediamiands (MDA) afterwards, stir and within 20 minutes, put into MDI reaction again, add catalyst MB20 after reacting 30 minutes and continue reaction；
(3) MDI continuation reaction being continuously increased along with system viscosity are progressively added in midway, are gradually added required solvent DMF.Final viscosity controls 120-220Pa S/25 DEG C, and still temperature control is between 70 ~ 80 DEG C；
(4) reaction adds terminator methanol after terminating, and finally adds softening agent, modifier again；
(5) cool to 60 DEG C and be carried out below rushing down material, metering packing.
In order to verify synthetic leather not only soft, plentiful, the good springiness that the soft high-elasticity embossing sofa artificial leather Wet-type polyurethane resin of the present invention is made, moreover it is possible to meeting embossability, embossing pattern is clearly full, feel before and after embossing, can be kept to change the advantages such as little.Resin prepared in the embodiment above and the contrast of ordinary soft low modulus Wet-type polyurethane resin, the method known by synthetic leather industry is drawn a design.Survey through examination, with the wet method crust leather made by the resin of the embodiment above 1,2,3 preparation, soft plentiful, good springiness；And the wet method crust leather that ordinary soft low modulus Wet-type polyurethane resin is made, soft, but richness and elasticity are all general.Equally, with the wet method crust leather made by the resin of the embodiment above 1,2,3 preparation, it is easy to embossing, decorative pattern is clearly full, and before and after embossing, feel change is little；And the wet method crust leather that ordinary soft low modulus Wet-type polyurethane resin is made, energy embossing, but decorative pattern is not clearly full, and before and after embossing, feel changes greatly.
What is called system of the present invention, refers to whole reaction system, it is simply that the total amount of all substances.The present invention is not by the restriction of above-mentioned case study on implementation, described in the embodiment above and description is that principles of the invention is described, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements broadly fall within present invention scope.
Claims (6)
1. the preparation method of a soft high-elasticity embossing sofa leather wet-method polyurethane resin, it is characterised in that comprise the following steps:
(1) put into various PEPA and mixture thereof in a kettle., antioxidant I-1010, partial solvent DMF mix, quantitative di-isocyanate reaction is put into again after stirring 10-15 minute, the 90% of the reasonable stoichiometric of now quantitative diisocyanate, during pre-polymerization, solid content should control at 50-60%, still temperature control is at 70-80 DEG C, and the response time controlled at 60-80 minute；
(2) little molecule dihydroxylic alcohols that molecular weight is 62-200g/mol and diamine mixed chain extender are added after, under adding catalyst existent condition, with diisocyanate generation chain extending reaction, along with being continuously increased of system viscosity, being gradually added remaining solvent DMF, final viscosity controls 120-220Pa s/25 DEG C；
(3) reaction adds terminator methanol after terminating, and finally adds modifier and auxiliary agent, to improve the wet type processing characteristics of resin；
(4) cool to 60 DEG C and be carried out below rushing down material, metering packing；
Described PEPA and mixture thereof composed as follows: poly-adipic acid diglycol BDO esterdiol: number-average molecular weight is 3000 ± 300g/mol, accounts for the 70-100wt% of polyol blends；Poly-adipate glycol diglycol esterdiol: number-average molecular weight is 2000 ± 200g/mol, accounts for the 30-0wt% of polyol blends；Described PEPA and mixture thereof and little molecule dihydroxylic alcohols and diamine mixed chain extender mol ratio 1:1.5-2.5.
2. the preparation method of a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin according to claim 1, it is characterised in that the 0.1-0.2% that consumption is system gross weight of described antioxidant I-1010；The consumption of described solvent DMF is the 69-71% of system gross weight.
3. the preparation method of a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin according to claim 1, it is characterised in that described diisocyanate is 4,4 '-methyl diphenylene diisocyanate.
4. the preparation method of a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin according to claim 1, it is characterized in that, little molecule glycol chain extender selected from ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diamine chain extenders is selected from diphenylmethanediamiand, and it is 7-12:1 that dihydroxylic alcohols mixes molar ratio when using with diamine；The consumption of described dihydroxylic alcohols and diamine mixed chain extender accounts for the 1-2% of system gross weight.
5. the preparation method of a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin according to claim 1, it is characterised in that described catalyst is organo-bismuth class catalyst MB20, and consumption is the 0.1-1 ‰ of PEPA and mixture weight thereof；Described modifier is acetic acid butyl cellulose, and consumption is the 1-1.5% of system gross weight；Described auxiliary agent is one or both the mixture in softening agent, levelling agent, and consumption is the 2-3% of system gross weight.
6. the preparation method of a kind of soft high-elasticity embossing sofa leather wet-method polyurethane resin according to claim 1, it is characterized in that, described PEPA and mixture, diisocyanate, little molecule dihydroxylic alcohols and diamine mixed chain extender, solvent DMF all require that moisture content is less than 500ppm.
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| CN103804627B (en) * | 2014-02-19 | 2016-03-30 | 合肥安利聚氨酯新材料有限公司 | A kind of wet type high-peel-strength polyurethane resin and preparation method thereof |
| CN105111406A (en) * | 2015-09-14 | 2015-12-02 | 合肥安利聚氨酯新材料有限公司 | High-plasticity wet process polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof |
| CN105153399B (en) * | 2015-09-29 | 2018-04-10 | 合肥安利聚氨酯新材料有限公司 | A kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter and preparation method thereof |
| CN105199078A (en) * | 2015-10-08 | 2015-12-30 | 合肥安利聚氨酯新材料有限公司 | Medium-soft luggage leather embossing resin for elastic fabrics and preparation method thereof |
| CN106397716A (en) * | 2016-09-06 | 2017-02-15 | 上海华峰超纤材料股份有限公司 | Moisture absorption dyeable polyurethane resin and preparation method thereof |
| CN106883371A (en) * | 2017-03-23 | 2017-06-23 | 苏州富仁化工有限公司 | A kind of modified polyurethane resin and preparation method thereof |
| CN108894007A (en) * | 2018-06-15 | 2018-11-27 | 合肥安利聚氨酯新材料有限公司 | Sofa furniture class use for synthetic leather polyurethane cover resin |
| CN109666114A (en) * | 2018-12-11 | 2019-04-23 | 无锡双象超纤材料股份有限公司 | A kind of preparation method of Cambodia's sense woven fabric sofa artificial leather wet polyurethane resin |
| CN109853254B (en) * | 2019-02-28 | 2021-08-03 | 扬州工业职业技术学院 | Medium-hard mirror polyurethane wet base and preparation method thereof |
| CN110437410A (en) * | 2019-08-08 | 2019-11-12 | 合肥安利聚氨酯新材料有限公司 | A kind of soft easy embossing wet polyurethane resin of polyether-type and preparation method thereof |
| CN115260440B (en) * | 2022-08-16 | 2023-09-12 | 江苏华大新材料有限公司 | Polyurethane resin for wet embossing synthetic leather and preparation method thereof |
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