CN106750159A - The preparation method of high abrasion safety and industrial gloves polyurethane resin - Google Patents
The preparation method of high abrasion safety and industrial gloves polyurethane resin Download PDFInfo
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- CN106750159A CN106750159A CN201611095142.6A CN201611095142A CN106750159A CN 106750159 A CN106750159 A CN 106750159A CN 201611095142 A CN201611095142 A CN 201611095142A CN 106750159 A CN106750159 A CN 106750159A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Gloves (AREA)
Abstract
A kind of preparation method of high abrasion safety and industrial gloves polyurethane resin, comprises the following steps：(I) poly-dihydric alcohol and isocyanates are (0.5~2.0) according to the ratio of the molal quantity of the molal quantity and poly-dihydric alcohol of isocyanates: 1 ratio carries out prepolymerization reaction；(II) auxiliary agent and glycol chain extender are added, continuing heating makes prepolymer be reacted with glycol chain extender；(III) add isocyanates to continue to react, during the course of the reaction, solvent and auxiliary agent are gradually added into system；(IV) when predetermined viscosity is reached, small molecule monohydric alcohol terminating reaction is added, adds auxiliary agent and a small amount of solvent to stir.Due to first allowing poly-dihydric alcohol and a part of di-isocyanate reaction, the prepolymer of generation isocyanate groups end-blocking, make the soft section of polyurethane resin and hard section ordered arrangement, so as to control hardening of resin speed and cell size, and then control resin to gloves core ground penetration degree, it is unlikely to gloves hardly possible break away from moulds while reaching high abrasion again.
Description
Technical field
The present invention relates to a kind of preparation method of high abrasion safety and industrial gloves polyurethane resin, belong to synthetic leather field.
Background technology
Polyurethane safety and industrial gloves in the market is main to be obtained by base material immersion solvent type polyurethane of gloves core.It is this
Gloves have that rubber shoe latex layer is relatively thin, wear with it is comfortable, with preferable grease proofing, anti-wear performance, low cost and other advantages, so as in industrial or agricultural
The fields such as production, building, medical treatment are suffered from being widely applied, and are indispensable hand protection articles for use, and international city has been turned into recent years
Staple product in the safety gloves of field, sales volume constantly rises.With the improvement of people ' s living standards, people to appliances for labor protection also by
Gradually pursue high-quality.Polyurethane safety and industrial gloves in the market, particularly gloves core are the gloves of terylene material, anti-wear performance
Generally in level Four (8000 times) below, range of application and the application of safety and industrial gloves polyurethane resin are limited to a certain extent
Effect.Chinese patent CN201310078488.5 describes a kind of preparation method of use for synthetic leather high abrasion polyurethane resin, this
Method is the preparation method of dry method resin.
The content of the invention
It is a kind of high resistance to the purpose of the present invention is to propose to a kind of preparation method of the wet method resin exclusively for PU safety and industrial gloves
The preparation method of safety and industrial gloves polyurethane resin is ground, makes polyurethane safety and industrial gloves that there is excellent anti-wear performance.
The preparation method of this high abrasion safety and industrial gloves polyurethane resin is comprised the following steps：
(I) by poly-dihydric alcohol and isocyanates in solvent dimethylformamide according to the molal quantity and poly- two of isocyanates
The ratio of the molal quantity of first alcohol is (0.5~2.0): 1 ratio carries out prepolymerization reaction；
(II) auxiliary agent and glycol chain extender are added, continuing heating makes prepolymer be reacted with glycol chain extender；
(III) add isocyanates to continue to react, during the course of the reaction, solvent and auxiliary agent are gradually added into system；
(IV) viscosity of resin is detected, when reaching 2.2 × 105~2.6 × 105At mPas/25 DEG C, small molecule one is added
First alcohol terminating reaction, adds auxiliary agent and a small amount of solvent to stir；
In above-mentioned steps, the molal quantity of the poly-dihydric alcohol in the Ith step adds the molal quantity of the glycol chain extender in the IIth step
Sum is equal to the total mole number of isocyanates.
The preparation method of this high abrasion safety and industrial gloves polyurethane resin, first allows poly-dihydric alcohol and a part of two isocyanic acid
Ester reacts, the prepolymer of generation isocyanate groups end-blocking, makes in system without free diisocyanate, adds diol chain extender
Agent is reacted with prepolymer, controls to match holding alcoholic OH groups excess, is glued up to end-blocking finally by anti-diisocyanate of mending.
The method can make the soft section of polyurethane resin and hard section ordered arrangement, so as to control hardening of resin speed and cell size, enter
And resin is controlled to the penetration degree of gloves core.Fireballing performance requirement is washed for glove leather, the present invention uses hydrophily
Strong PEPA, the replacing velocity of N, N-dimethylformamide is accelerated with this, while keeping setting rate and washing speed
Between balance, so as to reach be unlikely to again while high abrasion gloves hardly possible break away from moulds.
Specific embodiment
The preparation method of this high abrasion safety and industrial gloves polyurethane resin is comprised the following steps：
(I) by poly-dihydric alcohol and isocyanates in solvent dimethylformamide according to the molal quantity and poly- two of isocyanates
The ratio of the molal quantity of first alcohol is (0.5~2.0): 1 ratio carries out prepolymerization reaction；
(II) auxiliary agent and glycol chain extender are added, continuing heating makes prepolymer be reacted with glycol chain extender；
(III) add isocyanates to continue to react, during the course of the reaction, solvent and auxiliary agent are gradually added into system；
(IV) viscosity of resin is detected, when reaching 2.2 × 105~2.6 × 105At mPas/25 DEG C, small molecule one is added
First alcohol terminating reaction, adds auxiliary agent and a small amount of solvent to stir；
The molal quantity of poly-dihydric alcohol adds the molal quantity sum of glycol chain extender in the IIth step to be equal to isocyanide in wherein the Ith step
The total mole number of acid esters.
In the preparation method of this high abrasion safety and industrial gloves polyurethane resin, described isocyanates can for 4,4 '-
The fragrant same clan's diisocyanate of methyl diphenylene diisocyanate, toluene di-isocyanate(TDI) equimolecular quantity less than 300g/mol
The mixture of one or more；The number-average molecular weight of described poly-dihydric alcohol is 500~4000g/mol；Described chain extender
Molecular weight is 62~500g/mol.
Auxiliary agent described in the preparation method of this high abrasion safety and industrial gloves polyurethane resin can be catalyst, antioxygen
Agent, stabilizer, cell modifiers etc..
In the preparation method of this high abrasion safety and industrial gloves polyurethane resin, the chain extender can be ethylene glycol, 1,
2- propane diols, methyl propanediol, 1,3-BDO, BDO, 1,6- hexylene glycols, 1,5 pentanediols, diethylene glycol, new penta
One or two in glycol.
Poly-dihydric alcohol can be polyester polyols described in the preparation method of this high abrasion safety and industrial gloves polyurethane resin
One or several mixing of alcohol, PPG.
In the preparation method of this high abrasion safety and industrial gloves polyurethane resin, the reaction temperature of step I can be controlled in 60
DEG C~90 DEG C, step II, III, IV reaction temperature can be controlled in 40 DEG C~90 DEG C.
Embodiment is described below：
Embodiment 1：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EA2000, antioxidant, DMF100g are added in reaction bulb, 50 DEG C is heated to and is stirred 30 minutes；
Input MDI 37.5g, are heated to 75 DEG C and react 2 hours.
(2) DMF200g, ethylene glycol 12g, control temperature 45 C is added to react 30 minutes；Divide 2 times and add remaining isocyanic acid
Ester, the 75 DEG C of reactions of control temperature, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction speed.In reaction
During increase the remaining DMF of addition with viscosity, then viscosity is detected, until viscosity reaches 2.2 × 105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 764g that solid content is 30%.
Embodiment 2：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-BA3000, antioxidant, DMF90g are added in reaction bulb, 50 DEG C is heated to and is stirred 30 minutes；
Input MDI 22.5g, are heated to 75 DEG C and react 2 hours.
(2) DMF250g, ethylene glycol 12g, control temperature 45 C is added to react 30 minutes；Divide 2 times and add remaining isocyanic acid
Ester, the 75 DEG C of reactions of control temperature, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction speed.In reaction
During increase the remaining DMF of addition with viscosity, then viscosity is detected, until viscosity reaches 2.2 × 105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 743g that solid content is 30%.
Embodiment 3：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EBA3000, antioxidant, DMF80g are added in reaction bulb, 50 DEG C is heated to and is stirred 30 minutes；
Input MDI25g, is heated to 75 DEG C and reacts 2 hours.
(2) DMF250g, butanediol 15g, control temperature 45 C is added to react 30 minutes；Divide 2 times and add remaining isocyanic acid
Ester, the 75 DEG C of reactions of control temperature, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction speed.In reaction
During increase the remaining DMF of addition with viscosity, then viscosity is detected, until viscosity reaches 2.2 × 105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 729g that solid content is 30%.
Embodiment 4：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EA2000, HP-BA2000, antioxidant, DMF120g are added in reaction bulb, 50 DEG C are heated to
Stirring 30 minutes；Input MDI30g, is heated to 75 DEG C and reacts 2 hours.
(2) DMF220g, ethylene glycol 11g, control temperature 45 C is added to react 30 minutes；Divide 2 times and add remaining isocyanic acid
Ester, the 75 DEG C of reactions of control temperature, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction speed.In reaction
During increase the remaining DMF of addition with viscosity, then viscosity is detected, until viscosity reaches 2.2 × 105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 749g that solid content is 30%.
Embodiment 5：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EBA3000, HP-EA2000, antioxidant, DMF110g are added in reaction bulb, 50 DEG C are heated to
Stirring 30 minutes；Input MDI30g, is heated to 75 DEG C and reacts 2 hours.
(2) DMF210g, ethylene glycol 10g, butanediol 3g, control temperature 45 C is added to react 30 minutes；Divide 2 additions surplus
Remaining isocyanates, the 75 DEG C of reactions of control temperature, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction
Speed.Increase the remaining DMF of addition with viscosity during the course of the reaction, then detect viscosity, 2.2 are reached until viscosity ×
105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 754g that solid content is 30%.
Embodiment 6：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EA3000, HP-BA3000, antioxidant, DMF80g are added in reaction bulb, 50 DEG C is heated to and is stirred
Mix 30 minutes；Input MDI17.5g, is heated to 75 DEG C and reacts 2 hours.
(2) DMF240g, ethylene glycol 8g, diethylene glycol 6g, control temperature 45 C is added to react 30 minutes；Divide 2 additions surplus
Remaining isocyanates, the 75 DEG C of reactions of control temperature, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction
Speed.Increase the remaining DMF of addition with viscosity during the course of the reaction, then detect viscosity, 2.2 are reached until viscosity ×
105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 741g that solid content is 30%.
Embodiment 7：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EBA3000, HP-BA2000, antioxidant, DMF100g are added in reaction bulb, 50 DEG C are heated to
Stirring 30 minutes；Input MDI23.3g, is heated to 75 DEG C and reacts 2 hours.
(2) DMF250g, butanediol 10g, diethylene glycol 6g, control temperature 45 C is added to react 30 minutes；Divide 2 additions
Remaining isocyanates, the 75 DEG C of reactions of control temperature, in 40 minutes each reaction time, it is anti-that centre adds 0.01g catalyst to accelerate
Answer speed.Increase the remaining DMF of addition with viscosity during the course of the reaction, then detect viscosity, 2.2 are reached until viscosity ×
105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 740g that solid content is 30%.
Embodiment 8：
(a) raw material proportioning
(b) preparation process
(1) dihydroxylic alcohols HP-EA3000, HP-BA2000, antioxidant, DMF70g are added in reaction bulb, 50 DEG C is heated to and is stirred
Mix 30 minutes；Input MDI27.8g, is heated to 75 DEG C and reacts 2 hours.
(2) DMF260g, ethylene glycol 8g, monoethanolamine 4g, control temperature 45 C is added to react 30 minutes；Divide 2 times and add residue
Isocyanates, control 75 DEG C of temperature reaction, 40 minutes each reaction time, centre adds 0.01g catalyst to accelerate reaction speed
Degree.Increase the remaining DMF of addition with viscosity during the course of the reaction, then detect viscosity, 2.2 are reached until viscosity ×
105mPa·s/25℃。
(3) methyl alcohol 0.20g reaction 150min are added, discharging obtains the polyurethane resin 756g that solid content is 30%.
Dihydroxylic alcohols HP-EA2000, HP-EA3000 in above-described embodiment are the homemade PEPA of applicant, and it is matched somebody with somebody
Side is ethylene glycol and adipic acid in molar ratio 1：1 ratio, its number-average molecular weight is respectively 2000,3000, and preparation method is row
Industry conventional method；Dihydroxylic alcohols HP-BA2000, HP-BA3000 in above-described embodiment are the homemade PEPA of applicant, its
It is BDO and adipic acid in molar ratio 1 to be formulated：1 ratio, its number-average molecular weight is respectively 2000,3000, preparation side
Method is industry conventional method；Dihydroxylic alcohols HP-EBA3000 in above-described embodiment is the homemade PEPA of applicant, and it is matched somebody with somebody
Side is ethylene glycol, BDO and adipic acid in molar ratio 1：1：2 ratio, its number-average molecular weight is 3000, preparation method
It is industry conventional method.
Polyurethane resin obtained by above-described embodiment is reinstated identical big with Changzhou Puffy spy's polyurethane resin PFT-311 mono-
Small terylene gloves core is made sample under similarity condition, carries out Martindale friction tests.Method of testing is as follows：
(1) 2 friction samples of a diameter of (38 ± 1) mm are cut from the diverse location of detected materials, by sample before test
21 ± 1 DEG C of temperature is statically placed in, can just be tested within more than 4 hours in the environment of relative humidity 65 ± 2%；
(2) sample is put into specimen holder, sample must be placed in specimen holder base center, and sample front is to be measured
One faces outwardly, and after being fixed with retainer ring, reuses spanner and locks specimen holder base；
(3) 100 mesh sand paper are taken to be placed on mill platform, then takes 2.5kg platens and be placed in mill platform centre position, install retainer ring simultaneously
Be locked screw；
(4) the specimen holder test of the good sample of device is placed face down on sand paper, takes counterweight, insert counterweight axostylus axostyle
Test in the circular groove of clamper, start test.
Result of the test
High abrasion safety and industrial gloves of the invention polyurethane resin embodiment sample and Changzhou Puffy spy's polyurethane resin
The Martindale friction test test results of PFT-311 are as follows：
| Title | Martindale friction number of times |
| The made safety and industrial gloves of embodiment 1 | 8524 |
| The made safety and industrial gloves of embodiment 2 | 8678 |
| The made safety and industrial gloves of embodiment 3 | 9246 |
| The made safety and industrial gloves of embodiment 4 | 9356 |
| The made safety and industrial gloves of embodiment 5 | 9832 |
| The made safety and industrial gloves of embodiment 6 | 10278 |
| The made safety and industrial gloves of embodiment 7 | 8865 |
| The made safety and industrial gloves of embodiment 8 | 9149 |
| The made safety and industrial gloves of PFT-311 | 6187 |
By Biao Ke get：The Martindale of the sample obtained by 8 embodiments rubs number of times more than 8000 times, i.e., wear-resisting super
Cross level Four；Compared compared with PFT-311, it is wear-resisting to be obviously improved.
Claims (5)
1. a kind of preparation method of high abrasion safety and industrial gloves polyurethane resin, it is characterised in that comprise the following steps：
(I) by poly-dihydric alcohol and isocyanates in solvent dimethylformamide according to the molal quantity and poly-dihydric alcohol of isocyanates
Molal quantity ratio be (0.5~2.0): 1 ratio carries out prepolymerization reaction；
(II) auxiliary agent and glycol chain extender are added, continuing heating makes prepolymer be reacted with glycol chain extender；
(III) add isocyanates to continue to react, during the course of the reaction, solvent and auxiliary agent are gradually added into system；
(IV) viscosity of resin is detected, when reaching 2.2 × 105~2.6 × 105At mPas/25 DEG C, small molecule monohydric alcohol is added
Terminating reaction, adds auxiliary agent and a small amount of solvent to stir；
The molal quantity of poly-dihydric alcohol adds the molal quantity sum of glycol chain extender in the IIth step to be equal to isocyanates in wherein the Ith step
Total mole number.
2. the preparation method of high abrasion safety and industrial gloves polyurethane resin as claimed in claim 1, it is characterised in that described
Poly-dihydric alcohol number-average molecular weight is 500~4000g/mol；Described isocyanates is aromatic series of the molecular weight less than 300g/mol
The mixture of one or more of class diisocyanate；The molecular weight of described glycol chain extender is 62~500g/mol.
3. the preparation method of high abrasion safety and industrial gloves polyurethane resin as claimed in claim 2, it is characterised in that described
Isocyanates is 4,4 '-methyl diphenylene diisocyanate or toluene di-isocyanate(TDI), the poly-dihydric alcohol be PEPA,
PPG one or several mixture, described glycol chain extender is ethylene glycol, 1,2-PD, methyl-prop two
One kind or two in alcohol, 1,3-BDO, BDO, 1,6- hexylene glycols, 1,5 pentanediols, diethylene glycol, neopentyl glycol
Kind.
4. a kind of preparation method of high abrasion safety and industrial gloves polyurethane resin as claimed in claim 3, it is characterised in that step
At 60 DEG C~90 DEG C, step II, III, IV reaction temperature are controlled at 40 DEG C~90 DEG C for rapid I reaction temperature control.
5. the preparation method of high abrasion safety and industrial gloves polyurethane resin as claimed in claim 4, it is characterised in that described
Auxiliary agent is catalyst, antioxidant, stabilizer, cell modifiers.
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| CN201611095142.6A CN106750159A (en) | 2016-12-02 | 2016-12-02 | The preparation method of high abrasion safety and industrial gloves polyurethane resin |
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| CN108250399A (en) * | 2017-12-01 | 2018-07-06 | 上海汇得科技股份有限公司 | A kind of high demoulding, excellent wear resistance safety and industrial gloves wet polyurethane resin and preparation method |
| CN109912761A (en) * | 2019-01-24 | 2019-06-21 | 扬州工业职业技术学院 | A kind of extra soft polyurethane wet process bass and preparation method thereof |
| CN110423459A (en) * | 2019-07-31 | 2019-11-08 | 上海深禾聚合物材料有限公司 | The preparation method of zero DMF dipped gloves aqueous PU glue |
| EP3772519A1 (en) * | 2019-08-07 | 2021-02-10 | Covestro Deutschland AG | Method for the production of polyurethane polymers which can be processed thermoplastically |
| CN112694589A (en) * | 2019-10-23 | 2021-04-23 | 科思创知识产权两合公司 | Polyurethane polymers having a hardness of less than or equal to 60 Shore A |
| EP3812410A1 (en) * | 2019-10-23 | 2021-04-28 | Covestro Intellectual Property GmbH & Co. KG | Polyurethane polymer having a hardness of 60 shore a or lower and good abrasion resistance |
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| CN109912761A (en) * | 2019-01-24 | 2019-06-21 | 扬州工业职业技术学院 | A kind of extra soft polyurethane wet process bass and preparation method thereof |
| CN110423459A (en) * | 2019-07-31 | 2019-11-08 | 上海深禾聚合物材料有限公司 | The preparation method of zero DMF dipped gloves aqueous PU glue |
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| EP3812410A1 (en) * | 2019-10-23 | 2021-04-28 | Covestro Intellectual Property GmbH & Co. KG | Polyurethane polymer having a hardness of 60 shore a or lower and good abrasion resistance |
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| EP3812407A1 (en) * | 2019-10-23 | 2021-04-28 | Covestro Deutschland AG | Polyurethane polymer having a <= 60 shore a hardness |
| US11787936B2 (en) | 2019-10-23 | 2023-10-17 | Covestro Intellectual Property Gmbh & Co. Kg | Polyurethane polymer having a hardness of less than or equal to 60 shore A and good abrasion resistance |
| CN113817134A (en) * | 2021-09-25 | 2021-12-21 | 华大化学(安徽)有限公司 | Polyurethane resin for air-permeable and moisture-permeable labor protection gloves and preparation method thereof |
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