CN102746484A - Preparation method of solvent-based dyeable wet polyurethane resin - Google Patents
Preparation method of solvent-based dyeable wet polyurethane resin Download PDFInfo
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Abstract
The invention provides a preparation method of a solvent-based dyeable wet polyurethane resin, comprising the following steps: introducing a group into polyurethane molecules to let the reacted polyurethane contain the group; and then establishing chemical bond between the polyurethane resin and dye molecules. The invention mainly aims at the problem that difficulty in coloring polyurethane and low color fastness after coloring in the existing dyeing process of non-figured islands-in-sea microfiber synthetic leather. The invention discloses a synthesis and preparation method of the polyurethane resin with good dyeing performance and obviously improved dyeing color fastness. According to the invention, after dyeing the non-figured islands-in-sea microfiber synthetic leather prepared by using the resin, the color fastness is raised 0.5-1.5 grade as against that of conventional polyurethane, the color is bright, the dyeing uniformity is raised, the dye application amount is reduced, the dyeing technology is simplified, and the invention has high application value and economic value.
Description
Technical field
The present invention relates to the MOLECULE DESIGN and preparation method that a kind of MOLECULE DESIGN of polyurethane resin and preparation method, particularly woven fabric high-performance can dye wet polyurethane resin.
Background technology
Current solvent-borne type super fiber leather wet polyurethane resin is all largely to block to stop a fluid polyurethane resin of reaction using methanol, and its main raw material(s) has：Middle high molecular weight polyols --- its molecular weight（Signified molecular weight of the invention is number-average molecular weight）For 500 ~ 5000, more preferred molecular weight is 1000 ~ 3000,4,4- methyl diphenylene diisocyanates（Abbreviation MDI）, ethylene glycol, solvent be dimethylformamide（Abbreviation DMF）, antioxidant, end-capping reagent（Methanol）, preservative, bleeding agent, emulsifying agent etc..
Indefinite island super fiber leather non-woven fabrics is impregnated with using the wet polyurethane, after solidification, decrement, sizing, in dyeing course, because common polyurethane resin dyeability is poor, dye molecule is difficult to enter into polyurethane molecular or can not carried out with polyurethane molecular chemical bonds, but largely adsorb in the hole of polyurethane or polyurethane resin surface.After repeatedly washing, its dye molecule is still largely rested on the hole and polyurethane surface of polyurethane, dyestuff is difficult to enter into polyurethane resin, cause the dye molecule in polyurethane molecular very rare, its fiber color is deep after super fiber leather is dyed, polyurethane is of light color, and polyurethane and fiber color difference cause dyeing defect very much greatly, the low disadvantage of color fastness.It is more complicated that microfiber synthetic leather its color after dyeing is not bright-coloured enough, color fastness is low, dyestuff consumes big, dyeing control, and easily dyeing speck etc. occurs.
The content of the invention
In order to solve the above problems, the preparation method of wet polyurethane resin can be dyed the invention provides a kind of solvent-borne type for enabling polyurethane resin and dye molecule to carry out chemical bonds, so as to improve the stainability energy of polyurethane in superfine fiber chemical leather by improving the dyeability of wet polyurethane, the dyeability of whole super fiber leather is then improved.
To achieve the above object, technical solution of the present invention is：
A kind of solvent-borne type can dye the preparation method of wet polyurethane resin, and its raw material at least includes middle high molecular weight polyols, 4,4- methyl diphenylene diisocyanates, ethylene glycol, solvent, antioxidant, end-capping reagent（Methanol）, preservative, bleeding agent, emulsifying agent；Its core scheme is introduced in polyurethane molecularGroup so that contain in reacted polyurethane
Group；Then polyurethane resin and dye molecule is enable to carry out chemical bonds.
Introduced in polyurethane molecular
The method of group is to use the polyalcohol with acylamino- as reaction medium；Wherein by percentage to the quality, the PTMG containing 40-60% in polyalcohol.
The preferred polytetrahydrofuran diol of polyalcohol（PTMG）, polycaprolactone glycol（PCL）, PCDL（PC）, polyester-diol（PE）In one or more.
Polyalcohol is mainly using such as：Polytetrahydrofuran diol（PTMG）, polycaprolactone glycol（PCL）, PCDL（PC）, polyester-diol（PE）Deng.
Polytetrahydrofuran diol molecular weight is generally 500 ~ 5000, and conventional molecular weight is 850 ~ 3000, and the most frequently used has PTMG1000, PTMG2000 and PTMG3000, preferably PTMG2000, PTMG3000.
Polycaprolactone glycol 500 ~ 5000, conventional molecular weight is 850 ~ 3000, and the most frequently used has PCL1000, PCL2000 and PCL3000, preferably PCL2000.
PCDL（PC）, conventional molecular weight is 850 ~ 3000, and the most frequently used has PC1000, PC2000 and PC3000, preferably PC2000.
Polyester-diol is adipic acid system PEPA, such as：PBA1000, PBA2000, PBA3000 etc. obtained by adipic acid and butanediol reaction,.Or be PEA1000, PEA2000, PEA3000 etc. obtained by adipic acid and glycol reaction, or adipic acid and PHA1000, PHA2000, PHA3000 of hexylene glycol reaction etc., either adipic acid mixes other organic acids and polyester system obtained by mixing glycol reaction, may be used among the present invention.It is preferred that PBA2000, PBA3000, PEA2000 and PHA2000.
The isocyanates that super fiber leather wet method resin is used, current predominantly MDI, non yellowing type polyurethane is such as：HDI systems, H12MDI ties up to the country and not used also.
The prioritization scheme of this preparation method can add amine chain extender in the reaction.
The chain extender can also be：Ethylene glycol（EG）, butanediol（1,4-BD）, hexylene glycol（1,6-HD）, MEA（MEA）, ethylenediamine（EA）, hexamethylene diamine（HA）, different Fu Er ketone diamines（IPDA）, 4,4- MDAs（MDA）, 4,4- diamino-dicyclohexyl methanes（H12MDA）In one kind；It is preferred that EG, 1,4-BD, EA, 4,4- MDA（MDA）, 4,4- diamino-dicyclohexyl methanes（H12MDA）In one kind；More preferably EG, MEA, EA, 4,4- MDA（MDA）In one kind.
Above-mentioned technical proposal is beneficial in that：
Using the stainability wet polyurethane resin of the present invention, the disadvantage that conventional polyurethanes resin is brought can be fundamentally solved, production cost can be substantially reduced, and the price of polyurethane resin is suitable or lower slightly with wet polyurethane price with conventional woven fabric.As can be seen here, can dye wet polyurethane resin has obvious price advantage and application advantage.
The present invention is primarily directed to currently not island ultrafine fiber synthetic leather（Referred to as：Super fiber leather）In dyeing course, polyurethane is difficult the color fastness after colouring, and colouring than relatively low, and the present invention is developed it is a there is good dyeability, and dyeing color fastness has synthesis and the preparation method of a kind of polyurethane resin significantly improved.Using the standby super fiber leather of the resin-made it is dyed after, its color fastness than using conventional polyurethanes prepare dyeing super fiber leather color fastness raising 0.5 ~ 1.5 grade, its color is more bright-coloured, dyeing uniformity is high, dyestuff usage amount is low, and dyeing is fairly simple, with very high application value and economic value.
Embodiment
Present invention is further described with reference to specific embodiment.The every research and development person of experimental condition of the present invention can need to adjust accordingly according to the design of oneself, and be not limited to the experimental condition of the present embodiment.
Embodiment 1
Specific proportioning and process conditions such as table 1,
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG2000 | 195 | （1）~（2）After addition, heat up and stir, dissolve PTMG, after dissolving is good, stir 30 minutes |
| （3） | MDI | 12.2 | Add（3）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （4） | DMF | 200 | Add（4）Dilution |
| （5） | EG | 15 | |
| （6） | MEA | 4 | （5）（6）Add, and stir 30 minutes together, add MDI |
| （7） | MDI | 85 | It is added portionwise |
| （8） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （9） | DMF | 330 | |
| （10） | End-capping reagent | In right amount | Add（9）With（10）, make reaction terminating, viscosity 160Pas, solid part is 30 ± 1% |
Embodiment 2
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG2000 | 100 | |
| （3） | PTMG3000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 80 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 19 | It is disposable to add（6）, and it is warming up to 80 DEG C of reaction 30min |
| （7） | MDI | 85 | It is added portionwise, 60min is reacted at 80 DEG C after every batch of addition |
| （8） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （9） | DMF | 330 | |
| （10） | MEA is blocked | In right amount | Add（10）, make reaction terminating, viscosity 160Pas, solid part is 30 ± 1% |
Embodiment 3
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG2000 | 100 | |
| （3） | PCL2000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | EA | 4 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 85 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| (11) | Methanol | In right amount | Add（10）(11) reaction terminating, viscosity 160Pas, are made, solid part is 30 ± 1% |
Embodiment 4
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG3000 | 100 | |
| （3） | PCL3000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | MDA | 8 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 85 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| 11 | End-capping reagent | In right amount | Add（10）(11) reaction terminating, viscosity 160Pas, are made, solid part is 30 ± 1% |
Embodiment 5
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG2000 | 100 | |
| （3） | PC2000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | H12MDA | 12 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 85 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| 11 | End-capping reagent | In right amount | Add（10）(11) reaction terminating, viscosity 160Pas, are made, solid part is 30 ± 1% |
Embodiment 6
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG3000 | 100 | |
| （3） | PC3000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 22 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | EA | 4 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 75 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| （11） | End-capping reagent | In right amount | Add（10）(11) reaction terminating, viscosity 160Pas, are made, solid part is 30 ± 1% |
Embodiment 7
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG2000 | 100 | |
| （3） | PBA2000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 18 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | MDA | 12 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 78 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| （11） | End-capping reagent | In right amount | Add（10）(11) reaction terminating, viscosity 160Pas, are made, solid part is 30 ± 1% |
Embodiment 8
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG3000 | 100 | |
| （3） | PBA3000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | MEA | 4 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 85 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| （11） | End-capping reagent | In right amount | Add（10）With（11）, make reaction terminating, viscosity 160Pas, solid part is 30 ± 1% |
Embodiment 9
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG2000 | 100 | |
| （3） | PEA2000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | MEA | 4 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 85 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| （11） | End-capping reagent | In right amount | Add（10）With（11）, make reaction terminating, viscosity 160Pas, solid part is 30 ± 1% |
Embodiment 10
| Sequence number | Material name | Consumption/g | Technological requirement |
| （1） | DMF | 200 | |
| （2） | PTMG3000 | 100 | |
| （3） | PHA2000 | 95 | （1）~（3）After addition, heat up and stir, be uniformly dissolved PTMG, after dissolving is good, stir 30 minutes |
| （4） | MDI | 12.2 | Add（4）Afterwards, 70 DEG C of reaction 60min are slowly warming up to |
| （5） | DMF | 200 | After reaction time arrives, add（5）Dilution |
| （6） | EG | 15 | |
| （7） | MEA | 4 | （6）（7）Add, and stir 30 minutes together, add MDI |
| （8） | MDI | 85 | It is added portionwise |
| （9） | MDI | In right amount | Add in batches, increase viscosity, reach process viscosity |
| （10） | DMF | 330 | |
| （11） | End-capping reagent | In right amount | Add（10）With（11）, make reaction terminating, viscosity 160Pas, solid part is 30 ± 1% |
The present invention is from polyurethane molecular structural analysis, find it is a kind of can strengthen polyurethane dyeing group, and then carry out MOLECULE DESIGN, and pass through common synthesis technique, it is excellent to prepare a kind of dyeability, the dyeing wet polyurethane resin that mechanics and chemical property and woven fabric conventional polyurethanes resin are close.
The fiber of domestic indefinite island super fiber leather is largely to use nylon 6（PA6）Come what is prepared, PA6 is polyamide structure, contain amide groups in molecular structure, can be by acid dyes, neutral dye and reactive dyeing, but ultra-fine nylon, thinner than general fibre, specific surface area is big, thus there are many special dyeabilities, such as dyeing rate is fast, colour rendering or depth are poor, level-dyeing property is poor, dyefastness difference.The general chemical structure of polyurethane is polyurethanes, and the block copolymer being made up of soft chain segment and hard segment can use disperse dyes, neutral dye and acid dyeing.The present invention is in line with a kind of and similar PA6 chemical group of searching, by being introduced in polyurethane resin and chemical group similar PA6, enable polyurethane resin and dye molecule chemical bonds, strengthen the dyeability of polyurethane resin, so as to improve dyeability and color fastness of whole super fiber leather etc..
The molecular structure or chemical group combined with premetallized dye molecule is not contained in conventional polyurethanes molecular machinery, during so as to cause to contaminate super fiber leather processed using premetallized dye, polyurethane resin can not carry out chemical bonds with dye molecule, therefore its color fastness and property bright in luster are all poor, if using with the polyurethane resin with dye molecule conjugated group, dyeing speck mentioned above can be fundamentally addressed.
Contain in nylon 6
Group, and contain in common polyurethane
Group, although the two sees very close on the surface, but from analysis of the molecular structure, nylon 6
There is active H atom, the active H atom easily can be chemically reacted by other chemical substance, and form chemical bond.But
H atom in group directly and other chemical bonds, therefore, chemical bonds can not be carried out during dyeing with dye molecule, and can only carry out Hydrogenbond.
According to above-mentioned analysis, we can contemplate introduces in polyurethane molecular
Group, and to introduce the group, it may be considered that the polyalcohol with acylamino-, such as polyethers or polyester-type, primary hydroxyl amido silicon oil or chain extender are using organic amine etc. so that contain in reacted polyurethane
Group.According to the selection of raw material and come source problem, and price problem etc., the present invention mainly meets the requirement of production application using amine chain extender.
Super fiber leather wet polyurethane, in order to meet the requirement of high physical property, its polyalcohol is mainly using such as：Polytetrahydrofuran diol（PTMG）, polycaprolactone glycol（PCL）, PCDL（PC）, polyester-diol（PE）Deng.
Polytetrahydrofuran diol has molecular weight to be generally 500 ~ 5000, and conventional molecular weight is 850 ~ 3000, and the most frequently used has PTMG1000, PTMG2000 and PTMG3000, preferably PTMG2000, PTMG3000.
Polycaprolactone glycol 500 ~ 5000, conventional molecular weight is 850 ~ 3000, and the most frequently used has PCL1000, PCL2000 and PCL3000, preferably PCL2000.
PCDL（PC）, conventional molecular weight is 850 ~ 3000, and the most frequently used has PC1000, PC2000 and PC3000, preferably PC2000.
Polyester-diol is generally adipic acid system PEPA, such as：PBA1000, PBA2000, PBA3000 etc. obtained by adipic acid and butanediol reaction.Or be PEA1000, PEA2000, PEA3000 etc. obtained by adipic acid and glycol reaction, or adipic acid and PHA1000, PHA2000, PHA3000 of hexylene glycol reaction etc., either adipic acid mixes other organic acids and polyester system obtained by mixing glycol reaction, may be used among the present invention.It is preferred that PBA2000, PBA3000, PEA2000 and PHA2000.
The isocyanates that super fiber leather wet method resin is used, current predominantly MDI, non yellowing type polyurethane is such as：HDI systems, H12MDI ties up to the country and not used also.
Chain extender has：Ethylene glycol（EG）, butanediol（1,4-BD）, hexylene glycol（1,6-HD）, MEA（MEA）, ethylenediamine（EA）, hexamethylene diamine（HA）, different Fu Er ketone diamines（IPDA）, 4,4- MDAs（MDA）, 4,4- diamino-dicyclohexyl methanes（H12MDA）Deng.It is preferred that EG, 1,4-BD, EA, 4,4- MDA（MDA）, 4,4- diamino-dicyclohexyl methanes（H12MDA）, more preferably EG, MEA, EA, 4,4- MDA（MDA）.
Invention test procedure：
In the case of a certain amount of DMF, the polyalcohol of all meterings is added, MDI is added according to polyalcohol molal quantity 50 ~ 95%, reacted 60 ~ 90 minutes at 70 ~ 90 DEG C, a certain amount of DMF dilutions are then added, after stirring, add chain extender, after stirring reaction 30 minutes, MDI is added portionwise, resin viscosity is reached technological requirement, end-capping reagent is added when reaching process viscosity, stop reaction, and add part DMF to be cooled to 50 DEG C after adjusting viscosity and solid part, stirring 30min with bottom discharge.Its thermal oxidation resistance agent, catalyst, end-capping reagent etc., can select conven-tional adjuvants, dyeability and performance to resin have not significant impact, will not be described further here.
In order to ensure all to add about 50% in the elasticity and flexibility of resin, resin（The mass percent of whole polyalcohol is accounted for, similarly hereinafter）PTMG, in order to which the resin prepared by all formulas has uniformity, at the same in order to avoid polyalcohol the influence to resin of species and chain extender and carry out follow-up proportioning adjustment, the MDI amounts that all resins are used all immobilize.
Claims (11)
1. a kind of solvent-borne type can dye the preparation method of wet polyurethane resin, it is characterised in that：Introduced in polyurethane molecular
Group so that contain in reacted polyurethane
Group；Then polyurethane resin and dye molecule is enable to carry out chemical bonds.
2. a kind of solvent-borne type as claimed in claim 1 can dye the preparation method of wet polyurethane resin, it is characterised in that：Introduced in polyurethane molecular
The method of group is to use the polyalcohol with acylamino- as reaction medium.
3. a kind of solvent-borne type as claimed in claim 2 can dye the preparation method of wet polyurethane resin, it is characterised in that：By percentage to the quality, the PTMG containing 40-60% in polyalcohol.
4. a kind of solvent-borne type as claimed in claim 2 can dye the preparation method of wet polyurethane resin, it is characterised in that：The preferred polytetrahydrofuran diol of polyalcohol（PTMG）, polycaprolactone glycol（PCL）, PCDL（PC）, polyester-diol（PE）In one or more.
5. a kind of solvent-borne type as claimed in claim 4 can dye the preparation method of wet polyurethane resin, it is characterised in that：
The polytetrahydrofuran diol uses one kind in PTMG1000, PTMG2000 and PTMG3000, and its molecular weight is 500 ~ 5000；
The polycaprolactone glycol uses one kind in PCL1000, PCL2000 and PCL3000, and its molecular weight is 500 ~ 5000；
The PCDL（PC）Its molecular weight is one kind in 850 ~ 3000, preferably PC1000, PC2000 and PC3000；
The polyester-diol is adipic acid system PEPA.
6. a kind of solvent-borne type as claimed in claim 5 can dye the preparation method of wet polyurethane resin, it is characterised in that：
The polytetrahydrofuran diol molecular weight preferably 850 ~ 3000, preferably PTMG2000, PTMG3000；
The polycaprolactone glycol, molecular weight preferably 850 ~ 3000, preferably PCL2000；
The PCDL（PC）It is preferred that PC2000, molecular weight preferably 850 ~ 3000；
Described polyester-diol preferred PBA2000, PBA3000, PEA2000 and PHA2000.
7. a kind of solvent-borne type as claimed in claim 1 can dye the preparation method of wet polyurethane resin, it is characterised in that：Amine chain extender is added in reaction.
8. a kind of solvent-borne type described in claim 7 can dye the preparation method of wet polyurethane resin, it is characterised in that：The chain extender can also be：Ethylene glycol（EG）, butanediol（1,4-BD）, hexylene glycol（1,6-HD）, MEA（MEA）, ethylenediamine（EA）, hexamethylene diamine（HA）, different Fu Er ketone diamines（IPDA）, 4,4- MDAs（MDA）, 4,4- diamino-dicyclohexyl methanes（H12MDA）In one kind.
9. a kind of solvent-borne type described in claim 8 can dye the preparation method of wet polyurethane resin, it is characterised in that：Preferred EG, 1,4-BD, EA, 4,4- MDA of described chain extender（MDA）, 4,4- diamino-dicyclohexyl methanes（H12MDA）In one kind.
10. a kind of solvent-borne type described in claim 9 can dye the preparation method of wet polyurethane resin, it is characterised in that：Described chain extender is more preferably EG, MEA, EA, 4,4- MDA（MDA）In one kind.
11. a kind of solvent-borne type as claimed in claim 1 can dye the preparation method of wet polyurethane resin, it is characterised in that：Its raw material at least includes middle high molecular weight polyols, 4,4- methyl diphenylene diisocyanates（MDI）, ethylene glycol, solvent, antioxidant, end-capping reagent（Methanol）, preservative, bleeding agent, emulsifying agent.
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| CN104163909A (en) * | 2014-08-06 | 2014-11-26 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof |
| CN104356350A (en) * | 2014-11-12 | 2015-02-18 | 超然(福建)新材料科技有限公司 | High-dyeability polyurethane resin and preparation method thereof |
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| CN104163909A (en) * | 2014-08-06 | 2014-11-26 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof |
| CN104356350A (en) * | 2014-11-12 | 2015-02-18 | 超然(福建)新材料科技有限公司 | High-dyeability polyurethane resin and preparation method thereof |
| CN105542108A (en) * | 2015-12-22 | 2016-05-04 | 上海华峰超纤材料股份有限公司 | Easily-dyeable polyurethane resin used for superfine fiber synthetic leather and preparation method thereof |
| CN105801813B (en) * | 2016-04-29 | 2019-10-08 | 浙江枧洋高分子科技有限公司 | Polyurethane resin for superfine fibre soaking and preparation method thereof |
| CN110952335A (en) * | 2018-09-26 | 2020-04-03 | 上海华峰超纤材料股份有限公司 | Weather-resistant island-fixing fiber base cloth and preparation method and application thereof |
| CN110952335B (en) * | 2018-09-26 | 2022-07-01 | 上海华峰超纤科技股份有限公司 | Weather-resistant island-fixing fiber base cloth and preparation method and application thereof |
| CN111733616A (en) * | 2020-06-29 | 2020-10-02 | 旭川化学（苏州）有限公司 | Polyurethane resin for polyester fixed island microfiber and preparation method thereof |
| WO2022001690A1 (en) * | 2020-06-29 | 2022-01-06 | 旭川化学（苏州）有限公司 | Polyurethane resin for terylene figured sea-island superfine fiber, and preparation method therefor |
| CN111733616B (en) * | 2020-06-29 | 2022-12-16 | 旭川化学（苏州）有限公司 | Polyurethane resin for polyester fixed island microfiber and preparation method thereof |
| CN112341589A (en) * | 2020-10-29 | 2021-02-09 | 浙江禾欣科技有限公司 | Polyurethane resin for high color fastness and preparation method thereof |
| CN112341589B (en) * | 2020-10-29 | 2021-09-17 | 浙江禾欣科技有限公司 | Polyurethane resin for high color fastness and preparation method thereof |
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Inventor after: Zhang Zhe Inventor after: Sun Can Inventor after: Wu Huayuan Inventor after: Ran Bin Inventor after: Ding Huiyang Inventor before: Wu Huayuan Inventor before: Ding Huiyang Inventor before: Liu Wenhui Inventor before: Ran Bin |
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Application publication date: 20121024 |