CN102993398A - Wet type polyurethane resin, production process and application method thereof - Google Patents

Wet type polyurethane resin, production process and application method thereof Download PDF

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CN102993398A
CN102993398A CN201210395460XA CN201210395460A CN102993398A CN 102993398 A CN102993398 A CN 102993398A CN 201210395460X A CN201210395460X A CN 201210395460XA CN 201210395460 A CN201210395460 A CN 201210395460A CN 102993398 A CN102993398 A CN 102993398A
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polyurethane resin
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wet polyurethane
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CN102993398B (en
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李文国
黄志红
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Fujian Guobang New Material Co. Ltd.
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FUJIAN GUOBANG RESIN Co Ltd
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Abstract

The invention provides a wet type polyurethane resin, a production process and an application method thereof. The production process mainly comprises the following steps: 1, carrying out a soft-segment synthetic reaction on macromolecule dihydric alcohol and diphenyl methane diisocyanate; 2, enabling a first prepolymer to react; 3, adding a chain extender, and carrying out hard-segment synthetic reaction; and 4, adding an auxiliary. The wet type polyurethane resin manufactured by the production process is in form of yellowish transparent and thick viscous fluid, has viscosity of 180,000 to 220,000 (cps/25 DEG C), modulus of 100% under 4.5 to 5.5 Mpa, elongation of not less than 550% and strippability of not less than 12.0kg/3cm, the hydrolysis resistance is that 10% of NaOH is hydrated for 24 hours, and the wet type polyurethane resin has texture formation of 50 to 65%. The production process has the advantages that the texture formation, peeling strength and hydrolysis resistance of the wet type polyurethane resin are improved; the auxiliaries are selected before forming the leather, so that the density of the wet type polyurethane resin is improved, the finished artificial leather has washing durability and is high in strippability and full in touch.

Description

Wet polyurethane resin and production technique thereof and using method
Technical field
The present invention relates to a kind of chemical field, particularly a kind of wet polyurethane resin and production technique thereof and using method.
Background technology
At present, imitation leather all is to adopt traditional technique to carry out, and the leather that the produced urethane resin of traditional technology is used for being processed to form can not get high separability, becomes flesh good, the characteristic that hydrolysis is good
The size of leather abscess is relevant with the viscosity of leading portion performed polymer, and soft section of traditional technology and hard section are composite reaction, the bad control of many factors, and the leather abscess of making is little and regularity is poor, causes leather to become flesh not good, and stripping strength is not high.Need to improve the scraper number, increase the slurry usage quantity, just can reach relevant one-tenth flesh, to a certain degree increased cost.
For example, low whipping speed is less than normal, because reaction is inhomogeneous, the some places local reaction is fast, and what have is slow, and the product abscess of producing like this is with regard to skewness, so that stripping strength is not high.When stirring velocity was too fast, the velocity ratio of reacting in the production process was very fast, so that the abscess of leather is larger, also was unfavorable for the raising of stripping strength.
Equally, traditional technology is wanted so that viscosity reaches U in the prepolymerization reaction process of leading portion, and when temperature was hanged down, then speed of response was slow, and the time of production is long, and reaction is also insufficient; During excess Temperature, then the side reaction of reaction generation is many, and speed of response is too fast, and the bubble of generation is irregular, can not get the product of the high stripping performance of high-density.
In general original urethane resin adopts polyester polyol to synthesize mostly, and polyester polyol is formed by di-carboxylic acid and small molecular alcohol condensation, and reaction formula is as follows:
Figure 608166DEST_PATH_GDA00002734082000011
This reaction is reversible reaction under certain condition, can be found out by reaction formula, after leather is met water, within a certain period of time, polyester polyol can with the water generates reversed reaction so that product produces degraded, destroyed product itself, so its hydrolysis intensity of product of being produced by polyester polyol is bad.
Polyether glycol is the oligopolymer of end alkyl, and the alkyl on the main chain is connected by ehter bond.Polyether glycol be compound take low molecular weight polyols, polyamine or reactive hydrogen as initiator, form with olefin oxide ring-opening polymerization under catalyst action:
Figure 525306DEST_PATH_GDA00002734082000021
N in the formula---the polymerization degree
X---functionality
YH---its beginning agent
R---alkyl or hydrogen
Can be found out that by reaction formula polyether polyol is difficult for being degraded by being polymerized, and introduces polyether glycol in the PU synthetic leather, has significantly improved the anti-hydrolytic performance of product.But because the polarity of the ester bond in the relative polyester polyol of ehter bond that contains in the polyether polyol is little, when using the large polyester type of polarity as soft section, in macromole PU structure, more favourable to improving structural regularity and improving strength ratio.And adopt soft section of the little polyether-type of polarity, just poor aspect structural regularity and intensity.And polyether polyol contains side chain mostly, and these side chains can produce steric effect, so that hydrogen bond dies down between the PU molecular structure, and crystallinity deterioration, these stripping strength and tensile strength on product have direct impact.So on tensile strength and stripping strength index, adjust hydrolytic resistance, will select the few polyether glycol of side chain, and the consumption of polyether glycol need be controlled also.
Summary of the invention
The object of the present invention is to provide a kind of stripping strength high, become flesh good, the wet polyurethane resin that hydrolysis intensity is high and production technique thereof and using method.
The object of the present invention is achieved like this: it mainly may further comprise the steps: 1 macromolecule diol and diphenylmethanediisocyanate (MDI) carry out soft section building-up reactions, 2 first prepolymer reaction, 3 are added chainextender and carried out hard section building-up reactions; 4 add auxiliary agent.
The wet polyurethane resin that the present invention makes: its characteristic is: outward appearance is that little yellow transparent thickness is aqueous; Viscosity: 18-22 ten thousand (cps/25 ℃); 100% modulus 4.5-5.5Mpa; Tensile strength 〉=35Mpa; Elongation 〉=550%; Separability: 〉=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become flesh: 50~65%.
Utilize the method for wet polyurethane resin manufacture of intraocular leather to comprise that weight ratio is following: 100 parts of urethane (PU) resins, 10 ~ 14 parts of mill bases, teepol (GB-11) 0.5-1 part, 1 ~ 3 part of non-ionic surfactant (GB-7), DMF45-50 part.
The invention has the advantages that: the stirring velocity of soft section reaction in the building-up reactions of 1 adjustment diphenylmethanediisocyanate (MDI) and macromolecule diol, control suitable stirring velocity, temperature and reaction times.2. promote the first performed polymer viscosity, adjust the reaction times, temperature and the stirring velocity that reach required viscosity.Improve into flesh and stripping strength.3, in hard section reaction, having adopted symmetrical small molecules glycol is chainextender, has improved anti-hydrolytic performance and stripping strength, and 4 before leather forms, and for the selection of auxiliary agent, has improved the density of product, so that the feel of the imitation leather of final production is fuller.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
It mainly may further comprise the steps
It mainly may further comprise the steps: 1 product that macromolecule diol and diphenylmethanediisocyanate (MDI) are carried out soft section building-up reactions, 2 steps 1 carries out the first prepolymer reaction, 3 and adds chainextenders and carry out hard section building-up reactions, 4 and add auxiliary agents.
1, so-called soft section synthesizes and synthesizes after macromolecule diol and diphenylmethanediisocyanate (MDI) are put into solvent DMF (DMF) dissolving; Macromolecule diol, diphenylmethanediisocyanate (MDI) and the mixed weight of solvent (DMF) account for 37 ~ 39% of prescription gross weight, it is 30-35 rev/min than soft section synthetic reaction stirring velocity, temperature is controlled at 65-75 ℃, and the time was at 2 ~ 2.5 hours.
Macromolecule diol is: polyether glycol (PTMEG) and poly-hexanodioic acid Isosorbide-5-Nitrae butanediol ester (BA) and polyethylene glycol adipate (EA) in molar ratio example mix for 4:3:3.
2, the solvent that the product of building-up reactions is added prescription gross weight 13 ~ 17% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30-35 rev/min, temperature of reaction is 65-75 ℃, and the reaction times is 1.5 ~ 3 hours, obtains reacting viscosity at 10-15 ten thousand.
3, after the first prepolymer reaction is finished, in product, add the solvent of prescription gross weight 18 ~ 22% and add chainextender small molecules dibasic alcohol, carry out firmly section reaction after going forward side by side, hard section synthesizes synthesizing between small molecules dibasic alcohol and the diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: adding the small molecules dibasic alcohol below 50 ℃, stirring velocity rises to 40-45 rev/min, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to the 70-80 degree, temperature is controlled at 70-80 degree reaction 1 ~ 1.5 hour runs out of to MDI, wherein the chainextender weight of adding accounts for 1.5 ~ 2.5% of prescription production gross weight.
Described small molecules dibasic alcohol Isosorbide-5-Nitrae butyleneglycol; The interpolation mol ratio ratio of small molecules dibasic alcohol and macromolecule diol is between 2.0 ~ 3.0:1.
4, after the product urethane resin that really up to the mark section reaction generates adds the solvent of prescription gross weight 28 ~ 32% and adds auxiliary agent, stir, the addition of auxiliary agent be in the urethane resin prescription gross weight 0.5 ~ 0.8%.
Can make the product of following character by above-mentioned reaction, outward appearance is that little yellow transparent thickness is aqueous; Viscosity: 18-22 ten thousand (cps/25 ℃); 100% modulus 4.5-5.5Mpa; Tensile strength 〉=35Mpa; Elongation 〉=550%; Separability: 〉=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become flesh: 50~65%.
The present invention will be described below in conjunction with concrete experimental data
Case 1
Step is as follows:
1, so-called soft section synthesizes polyether glycol (PTMEG), poly-hexanodioic acid 1,4 butanediol esters (BA) and polyethylene glycol adipate (EA) are put into by mixture and the diphenylmethanediisocyanate (MDI) of mole 4:3:3 and are synthesized after the solvent DMF dissolves; Weight after macromolecule diol, diphenylmethanediisocyanate and the solvent accounts for 37% of prescription gross weight, and soft section synthetic reaction stirring velocity is 35 rev/mins, and temperature is controlled at 75 ℃, and the time was at 2 hours.
2, the solvent that the product of building-up reactions is added prescription gross weight 13% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 35 rev/mins, temperature of reaction is 75 ℃, and the reaction times is 1.5 hours, obtains soft section reaction viscosity 150,000.
3, after the first prepolymer reaction is finished, in product, add the solvent of prescription gross weight 22% and add chainextender small molecules dibasic alcohol, carry out firmly section reaction after going forward side by side, hard section synthesizes synthesizing between small molecules dibasic alcohol and the diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: adding the small molecules dibasic alcohol below 50 ℃, stirring velocity rises to 45 rev/mins, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70 degree, temperature is controlled at 70 degree reactions 1 hour runs out of to MDI, wherein the chainextender weight of adding accounts for 1.5% of reactant production gross weight.
4, after the product urethane resin that really up to the mark section reaction generates adds the solvent of prescription gross weight 32% and adds auxiliary agent, stir, the addition of auxiliary agent be in the urethane resin gross weight 0.8%.
The product property that this experiment is supported is as follows: outward appearance is that little yellow transparent thickness is aqueous; Viscosity: 220,000 (cps/25 ℃); 100% modulus 4.5Mpa; Tensile strength 〉=35Mpa; Elongation 〉=550%; Separability: 〉=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become flesh: 63%.
Embodiment 2
Step is as follows:
1, so-called soft section synthesizes polyether glycol (PTMEG), poly-hexanodioic acid 1,4 butanediol esters (BA) and polyethylene glycol adipate (EA) are put into by mixture and the diphenylmethanediisocyanate (MDI) of mole 4:3:3 and are synthesized after the solvent DMF dissolves; Weight after macromolecule diol, diphenylmethanediisocyanate and the solvent accounts for 33% of prescription gross weight, and soft section synthetic reaction stirring velocity is 30 rev/mins, and temperature is controlled at 65 ℃, and the time was at 2.5 hours.
2, the solvent that the product of building-up reactions is added prescription gross weight 15% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30 rev/mins, temperature of reaction is 65 ℃, and the reaction times is 2.5 hours, obtains soft section reaction viscosity 100,000.
3, after the first prepolymer reaction is finished, in product, add the solvent of prescription gross weight 20% and add chainextender small molecules dibasic alcohol, carry out firmly section reaction after going forward side by side, hard section synthesizes synthesizing between small molecules dibasic alcohol and the diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: adding the small molecules dibasic alcohol below 50 ℃, stirring velocity rises to 40 rev/mins, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70 degree, temperature is controlled at 70 degree reactions 1.5 hours runs out of to MDI, wherein the chainextender weight of adding accounts for 2.5% of reactant production gross weight.
4, after the product urethane resin that really up to the mark section reaction generates adds the solvent of prescription gross weight 28% and adds auxiliary agent, stir, the addition of auxiliary agent be in the urethane resin gross weight 0.5%.
The product property that this experiment is supported is as follows: outward appearance is that little yellow transparent thickness is aqueous; Viscosity: 180,000 (cps/25 ℃); 100% modulus 5.5Mpa; Tensile strength 〉=35Mpa; Elongation 〉=550%; Separability: 〉=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become flesh: 50%.
Embodiment 3
Step is as follows:
1, so-called soft section synthesizes polyether glycol (PTMEG), poly-hexanodioic acid 1,4 butanediol esters (BA) and polyethylene glycol adipate (EA) are put into by mixture and the diphenylmethanediisocyanate (MDI) of mole 4:3:3 and are synthesized after the solvent DMF dissolves; Weight after macromolecule diol, diphenylmethanediisocyanate and the solvent accounts for 35% of prescription gross weight, and soft section synthetic reaction stirring velocity is 30 rev/mins, and temperature is controlled at 70 ℃, and the time was at 2.3 hours.
2, the solvent that the product of building-up reactions is added prescription gross weight 15% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30 rev/mins, temperature of reaction is 70 ℃, and the reaction times is 2.0 hours, obtains soft section reaction viscosity 120,000.
3, after the first prepolymer reaction is finished, in product, add the solvent of prescription gross weight 20% and add chainextender small molecules dibasic alcohol, carry out firmly section reaction after going forward side by side, hard section synthesizes synthesizing between small molecules dibasic alcohol and the diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: adding the small molecules dibasic alcohol below 50 ℃, stirring velocity rises to 45 rev/mins, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70 degree, temperature is controlled at 70-80 degree reaction 1 hour runs out of to MDI, wherein the chainextender weight of adding accounts for 1.5% of reactant production gross weight.
4, after the product urethane resin that really up to the mark section reaction generates adds the solvent of prescription gross weight 30% and adds auxiliary agent, stir, the addition of auxiliary agent be in the urethane resin gross weight 0.56%.
The product property that this experiment is supported is as follows: outward appearance is that little yellow transparent thickness is aqueous; Viscosity: 200,000 (cps/25 ℃); 100% modulus 4.8Mpa; Tensile strength 〉=35Mpa; Elongation 〉=550%; Separability: 〉=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become flesh: 61%.
Use-pattern embodiment about this product is as follows:
Embodiment 4
It comprises that weight ratio is following: 100 parts of urethane (PU) resins, 12 parts of mill bases, 0.7 part of teepol (GB-11), 2 parts of non-ionic surfactants (GB-7), DMF45 part.
Embodiment 5
It comprises that weight ratio is following: 100 parts of urethane (PU) resins, 10 parts of mill bases, 1 part of teepol (GB-11), 3 parts of non-ionic surfactants (GB-7), DMF47 part.
Embodiment 6
It comprises that weight ratio is following: 100 parts of urethane (PU) resins, 14 parts of mill bases, 0.5 part of teepol (GB-11), 1 part of non-ionic surfactant (GB-7), DMF50 part.
With the slurry of handling well according to the above ratio, with the lining bar that is coated with in 1.2 millimeters gaps, be coated on the good non-woven fabrics of impregnation, left standstill 30 seconds, put into coagulating pan (aqueous solution of 20% left and right sides DMF), leave standstill and solidify 15 ~ 20 minutes.Good sample is solidified in taking-up, puts into washing bath (clear water), repeatedly pushes 8-10 time with pressure roller, cleans till the DMF in the sample.Sample is put into 120 ± 1 degree air dry ovens, and cooling is taken out in oven dry (20-30 minute), gets final product.

Claims (10)

1. the production technique of a wet polyurethane resin, it is characterized in that: it mainly may further comprise the steps: 1 product that macromolecule diol and diphenylmethanediisocyanate (MDI) are carried out soft section building-up reactions, 2 steps 1 carries out the first prepolymer reaction, 3 and adds chainextenders and carry out hard section building-up reactions; 4 add auxiliary agent.
2. the production technique of a kind of wet polyurethane resin according to claim 1, it is characterized in that: so-called soft section synthesizes and synthesizes after macromolecule diol and diphenylmethanediisocyanate (MDI) are put into the dissolving of solvent DMF; Weight after macromolecule diol, diphenylmethanediisocyanate and the solvent accounts for 37 ~ 39% of prescription gross weight, and soft section synthetic reaction stirring velocity is 30-35 rev/min, and temperature is controlled at 65-75 ℃, and the time was at 2 ~ 2.5 hours.
3. the production technique of a kind of wet polyurethane resin according to claim 1, it is characterized in that: the solvent that the product of building-up reactions is added prescription gross weight 13 ~ 17% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30-35 rev/min, temperature of reaction is 65-75 ℃, reaction times is 1.5 ~ 3 hours, obtains reacting viscosity at 10-15 ten thousand.
4. the production technique of a kind of wet polyurethane resin according to claim 1, it is characterized in that: after the first prepolymer reaction is finished, in product, add the solvent of prescription gross weight 18 ~ 22% and add chainextender small molecules dibasic alcohol, carry out firmly section reaction after going forward side by side, hard section synthesizes synthesizing between small molecules dibasic alcohol and the diphenylmethanediisocyanate; The condition of hard section reaction is: adding the small molecules dibasic alcohol below 50 ℃, stirring velocity rises to 40-45 rev/min, stir, add diphenylmethanediisocyanate, make its slow thermopositive reaction, after temperature rises to the 70-80 degree, temperature is controlled at 70-80 degree reaction 1 ~ 1.5 hour runs out of to MDI, wherein the chainextender weight of adding accounts for 1.5 ~ 2.5% of prescription production gross weight.
5. the production technique of a kind of wet polyurethane resin according to claim 2, it is characterized in that: described small molecules dibasic alcohol is the Isosorbide-5-Nitrae butyleneglycol; Macromolecule diol is: polyether glycol and poly-hexanodioic acid Isosorbide-5-Nitrae butanediol ester and polyethylene glycol adipate in molar ratio example mix for 4:3:3; The interpolation mol ratio ratio of small molecules dibasic alcohol and macromolecule diol is between 2.0 ~ 3.0:1.
6. the production technique of a kind of wet polyurethane resin according to claim 1, it is characterized in that: after the product urethane resin that really up to the mark section reaction generates adds the solvent of prescription gross weight 28 ~ 32% and adds auxiliary agent, stir, the addition of auxiliary agent be in the urethane resin prescription gross weight 0.5 ~ 0.8%.
7. according to claim 1 and 2 or the production technique of 3 or 6 described a kind of wet polyurethane resins, it is characterized in that: described solvent is DMF.
8. the production technique of a kind of wet polyurethane resin according to claim 6, it is characterized in that: described auxiliary agent is the fluorine high molecular synthetic resin.
9. wet polyurethane resin, it is characterized in that: outward appearance is that little yellow transparent thickness is aqueous; Viscosity: 18-22 ten thousand (cps/25 ℃); 100% modulus 4.5-5.5Mpa; Tensile strength 〉=35Mpa; Elongation 〉=550%; Separability: 〉=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become flesh: 50~65%.
10. method that adopts wet polyurethane resin manufacture of intraocular leather: it is characterized in that it comprises that weight ratio is following: 100 parts of urethane (PU) resins, 10 ~ 14 parts of mill bases, teepol (GB-11) 0.5-1 part, 1 ~ 3 part of non-ionic surfactant (GB-7), DMF45-50 part; With the slurry for preparing, with the lining bar that is coated with in 1.2 millimeters gaps, be coated on the good non-woven fabrics of impregnation, left standstill 30 seconds, put into coagulating pan (aqueous solution of 20% left and right sides DMF), leave standstill and solidify 15 ~ 20 minutes.Good sample is solidified in taking-up, puts into washing bath (clear water), repeatedly pushes 8-10 time with pressure roller, cleans till the DMF in the sample.Sample is put into 120 ± 1 degree air dry ovens, and cooling is taken out in oven dry (20-30 minute), gets final product.
CN201210395460.XA 2012-10-16 2012-10-16 Wet type polyurethane resin, production process and application method thereof Active CN102993398B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961880A (en) * 2015-07-14 2015-10-07 福建国邦树脂有限公司 Polyurethane binder resin for TPU film lamination
CN108468228A (en) * 2018-04-20 2018-08-31 齐鲁工业大学 A kind of ox hair powder filler is modified the preparation method of oiliness polyurethane wet bass
CN108641062A (en) * 2018-05-25 2018-10-12 清远市番亿聚氨酯有限公司 A kind of middle modulus, the preparation method of high springback wet method resin
CN111087566A (en) * 2019-09-29 2020-05-01 扬州工业职业技术学院 Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054435A (en) * 2007-04-26 2007-10-17 上海汇得树脂有限公司 Wet-type polyamine resin with hydrolyzation resistance and high peeling strength and preparing method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054435A (en) * 2007-04-26 2007-10-17 上海汇得树脂有限公司 Wet-type polyamine resin with hydrolyzation resistance and high peeling strength and preparing method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961880A (en) * 2015-07-14 2015-10-07 福建国邦树脂有限公司 Polyurethane binder resin for TPU film lamination
CN104961880B (en) * 2015-07-14 2018-08-24 福建国邦新材料有限公司 A kind of TPU membrane fitting polyurethane adhesive resin
CN108468228A (en) * 2018-04-20 2018-08-31 齐鲁工业大学 A kind of ox hair powder filler is modified the preparation method of oiliness polyurethane wet bass
CN108641062A (en) * 2018-05-25 2018-10-12 清远市番亿聚氨酯有限公司 A kind of middle modulus, the preparation method of high springback wet method resin
CN111087566A (en) * 2019-09-29 2020-05-01 扬州工业职业技术学院 Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin
CN111087566B (en) * 2019-09-29 2021-10-29 扬州工业职业技术学院 Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin

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Address after: 351117 Fujian city of Putian province high tech Industrial Development Zone, Fujian Guobang resin Co. Ltd.

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Address before: 351117 Fujian city of Putian province high tech Industrial Development Zone, Fujian Guobang resin Co. Ltd.

Patentee before: Fujian Guobang Resin Co., Ltd.