WO2024016667A1 - 一种浸胶手套用生物基浆料的制备方法 - Google Patents

一种浸胶手套用生物基浆料的制备方法 Download PDF

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WO2024016667A1
WO2024016667A1 PCT/CN2023/078426 CN2023078426W WO2024016667A1 WO 2024016667 A1 WO2024016667 A1 WO 2024016667A1 CN 2023078426 W CN2023078426 W CN 2023078426W WO 2024016667 A1 WO2024016667 A1 WO 2024016667A1
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glycol
preparation
mixture
weight
diisocyanate
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PCT/CN2023/078426
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English (en)
French (fr)
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陈�峰
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张家港思淇科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/0055—Plastic or rubber gloves
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00—Materials for garments
    • A41D2500/50—Synthetic resins or rubbers

Definitions

  • the invention relates to a preparation method of bio-based slurry for rubber-dipped gloves and the rubber-dipped gloves prepared by using the slurry, and belongs to the technical field of polymer materials.
  • PU coated gloves are also called PU rubberized gloves or PU dipped gloves and palm-fitting gloves.
  • the gloves are made of specially treated polyurethane that completely covers the palm part. They can provide good anti-slip performance and prevent sweat and sweat on the human palm. Particulate pollution.
  • the production process of ordinary PU dipped gloves has high carbon emissions. The degradation process of finished gloves is relatively slow, causing pollution to the environment.
  • bio-based polyurethane materials to replace ordinary PU materials.
  • bio-based slurry for dipping gloves Common bio-based materials are biopolymer materials or monomers obtained through bioconversion from renewable biomass such as cereals, legumes, straw, bamboo and wood powder, and then further polymerized to form environmentally friendly chemical products and green energy polymers. Material.
  • the existing bio-based slurry has a single component.
  • Rubber-impregnated gloves made from bio-based slurry are inferior in elasticity and cell size. After being made into gloves, they will feel stiff, have glue seepage on the back, and are wear-resistant. Poor flexibility and bending resistance.
  • the present invention provides a method for preparing bio-based slurry for dipping gloves, wherein the preparation method includes the following steps:
  • mixture B Add 80-100 parts by weight of biopolyurethane resin to mixture A prepared in S1, mix and stir to prepare mixture B;
  • the synthetic monomers of the bio-polyurethane resin are bio-based polyester diol and bio-based diphenylmethane-4,4'-diisocyanate;
  • the bio-polyester diol is a combination of succinic acid and 1,3 propylene glycol. polymer;
  • mixture C Add 0.5-1 parts by weight of wear-resistant and scratch-resistant agent to mixture B prepared in S2, mix and stir to prepare mixture C;
  • mixture D Add 0.01-0.05 parts by weight of Dow Corning OFS-6040 coupling agent to mixture C prepared in S3, and prepare mixture D through coupling; the viscosity of mixture D at room temperature drops. Enter the range of 500-700 centipoise;
  • mixture E Add 5-20 parts by weight of soft polyurethane resin to the mixture D prepared in S4, mix and stir to prepare the biological material for dipped gloves with a viscosity range of 800-1200 centipoise at room temperature. base slurry;
  • the synthetic monomers of the soft polyurethane resin are the first polyester diol, the second polyester diol and diphenylmethane-4,4’-diisocyanate;
  • the first polyester glycol is a polymer of polyadipic acid, 1,4-butanediol and ethylene glycol, with a number average molecular weight of 3000-5000g/mol; the second polyester glycol is polyethylene glycol.
  • the polymer of diacid and diethylene glycol has a number average molecular weight of 1500-2500g/mol; the weight ratio of the first polyester glycol to the second polyester glycol is 4-7:1.
  • the formula of the soft polyurethane resin includes the following components by weight:
  • the first glycol chain extender is ethylene glycol.
  • the synthesis process of the soft polyurethane resin includes:
  • Step a) and step b) are not in any order;
  • the formula of the biopolyurethane resin includes the following components by weight:
  • the first glycol chain extender is ethylene glycol; the second glycol chain extender is 1,4-butanediol.
  • the synthesis process of the biopolyurethane resin includes:
  • Step 1) Put 25% of the total mass of the biopolyester glycol and N,N'-dimethylformamide into the reaction kettle and mix evenly, raise the temperature to 40-45°C, and then put the diphenyl group into the reaction kettle. 18% of the total mass of methane-4,4'-diisocyanate, raise the temperature to 65-70°C, and react for 1-1.5 hours;
  • Step II Add 45% of the total mass of N,N'-dimethylformamide, the first glycol chain extender and the second glycol chain extender into the product of step I), The temperature dropped to 50-55°C, and after stirring for 1 hour, 70% of the total mass of diphenylmethane-4,4'-diisocyanate was added, the temperature was raised to 70-75°C, and the reaction was continued for 2-2.5 hours; then added The remaining diphenylmethane-4,4'-diisocyanate is added until the viscosity of the reactant reaches 350-400pa.s/50°C, and then the remaining N,N'-dimethylformamide is added to terminate the reaction to obtain the above Biopolyurethane resin.
  • the protein-imitating auxiliary agent is amino-modified silicone.
  • a 7.5kw high-speed mixer is used to perform the mixing and stirring operation.
  • the mixing blades of the high-speed mixer use a 300mm diameter dispersion disk, and the mixing speed is 800-1200 rpm.
  • the stirring speed in S3, S4 and S5 all falls within 400-700 rpm.
  • Another aspect of the present invention provides a rubber-dipped glove, wherein the rubber-dipped slurry used in the rubber-dipped gloves is prepared by the above-mentioned preparation method.
  • the invention provides a preparation method of bio-based slurry for rubber-dipped gloves and the rubber-dipped gloves produced by using the slurry; the rubber-dipped gloves produced by using the bio-based slurry of the present invention have better wear resistance and folding resistance. Excellent, better hand feel, more conducive to the commercial promotion and application of rubber-impregnated gloves products.
  • the formula of the bio-based slurry for dipping gloves in Example 1 is as follows (expressed in parts by weight):
  • the synthetic monomers of the biopolyurethane resin are biopolyester diol and diphenylmethane-4,4'-diisocyanate; the biopolyester diol is butanediol. Polymer of acid and 1,3 propylene glycol.
  • the formula of biopolyurethane resin includes the following components by weight:
  • the first glycol chain extender is ethylene glycol; the second glycol chain extender is 1,4-butanediol.
  • the synthesis process of the biopolyurethane resin includes:
  • Step 1) Put 25% of the total mass of the biopolyester glycol and N,N'-dimethylformamide into the reaction kettle and mix evenly, raise the temperature to 40-45°C, and then put the diphenyl group into the reaction kettle. 18% of the total mass of methane-4,4'-diisocyanate, raise the temperature to 65-70°C, and react for 1-1.5 hours;
  • Step II Add 45% of the total mass of N,N'-dimethylformamide, the first glycol chain extender and the second glycol chain extender into the product of step I), The temperature dropped to 50-55°C, and after stirring for 1 hour, 70% of the total mass of diphenylmethane-4,4'-diisocyanate was added, the temperature was raised to 70-75°C, and the reaction was continued for 2-2.5 hours; then added The remaining diphenylmethane-4,4'-diisocyanate is added until the viscosity of the reactant reaches 350-400pa.s/50°C, and then the remaining N,N'-dimethylformamide is added to terminate the reaction to obtain the above Biopolyurethane resin.
  • the synthetic monomers of the soft polyurethane resin are the first polyester diol, the second polyester diol and diphenylmethane-4,4'-diisocyanate;
  • the first polyester glycol is a polymer of polyadipic acid, 1,4-butanediol and ethylene glycol, with a number average molecular weight of 3000-5000g/mol;
  • the second polyester glycol is polyethylene glycol.
  • the polymer of acid and diethylene glycol has a number average molecular weight of 1500-2500g/mol; the weight ratio of the first polyester glycol to the second polyester glycol is 4-7:1.
  • the first polyester glycol is a polymer of polyadipic acid, 1,4-butanediol and ethylene glycol, with a number average molecular weight of approximately 4000g/mol;
  • the second polyester glycol is Diol is a polymer of polyadipic acid and diethylene glycol, with a number average molecular weight of 2000g/mol.
  • the formula of the soft polyurethane resin includes the following components by weight:
  • the first glycol chain extender is ethylene glycol.
  • the synthesis process of the soft polyurethane resin includes:
  • Step a) and step b) are not in any order;
  • the conventional cell regulator of polyurethane resin is used as the cell regulator.
  • amino-modified silicone is used as the imitation protein additive.
  • the wear-resistant and scratch-resistant agent is DC3289 product of Dow Corning.
  • Dow Corning's DC57 product is used as the defoaming agent.
  • the preparation method of bio-based slurry for rubber-dipped gloves in Example 1 includes the following steps:
  • mixture A Mix and stir the DMF solvent, imitation protein additive, amino-modified silicone oil and defoaming agent in the above formula to prepare mixture A;
  • DMF solvent, imitation protein additives, amino-modified silicone oil and defoaming agent are added to a mixing barrel (capacity specification is about 1000-2000L), and under high-speed stirring conditions of about 1000 rpm Mix and stir for about 30 minutes;
  • mixture B Add the above-mentioned biopolyurethane resin to mixture A prepared in S1, mix and stir to prepare mixture B;
  • a 7.5kw high-speed mixer is used to perform the mixing and stirring operation.
  • the mixing blades of the high-speed mixer use a 300mm diameter dispersion disk, and the mixing speed is 800-800 1200 rpm.
  • the above-mentioned biopolyurethane resin is added to the mixture A prepared in S1, and a 300mm diameter dispersion disk is used for mixing and stirring under high-speed stirring conditions of about 1000 rpm; during the stirring process, the viscosity
  • the measuring instrument monitors and measures the viscosity of mixture B (for example, every 5 minutes). When the viscosity of mixture B drops to 400-600 centipoise at room temperature, stop stirring.
  • mixture C Add the above-mentioned Dow Corning FBL-3289 to mixture B prepared in S2, mix and stir to prepare mixture C;
  • Dow Corning FBL-3289 is a conventional release feel agent and has better wear and scratch resistance. The inventor of this case tried a variety of feel agents and found that Dow Corning FBL-3289 has better fusion with bio-polyurethane resin. .
  • the stirring speed of S3 is controlled at about 500 rpm, and the temperature is controlled at 20°C-40°C.
  • mixture D Add Dow Corning OFS-6040 coupling agent to mixture C prepared in S3, and prepare mixture D through coupling; the viscosity of mixture D at normal temperature falls within 500-700 centimeters range of mooring;
  • the catalyst is added, stirred and mixed, the stirring speed is controlled at about 500 rpm, and the stirring is stopped after stirring for 5 minutes; then, mixture D is obtained after static reaction for 30 minutes.
  • mixture E Add soft polyurethane resin to mixture D prepared in S4, mix and stir to prepare the bio-based slurry for dipped gloves with a viscosity range of 800-1200 centipoise at room temperature;
  • the stirring speed is controlled at about 500 rpm and stirred for 30 minutes; during the stirring process, a viscosity measuring instrument is used to monitor and measure the viscosity of the obtained slurry (for example, every 5 minutes Measure), when the viscosity of the slurry drops to 800-1200 centipoise, stop stirring.
  • coloring slurry is added to the finally obtained bio-based slurry.
  • Example 1 Rubber-impregnated gloves using the bio-based slurry of Example 1
  • the production process of bio-impregnated gloves in Application Example 1 includes the following steps:
  • Step 1 Put the hand core body into the mold; put the nylon glove core or cut-proof glove core on the glove mold core respectively;
  • Step 2 Dip the hand core after molding. Dip the hand core after molding in step 1 into the bio-based slurry of Example 1, and stay for 1-5 seconds;
  • Step three the water washing section, uses cleaning water to clean the hand core after dipping;
  • Step 4 Drying after washing, use an oven to dry the washed hand core
  • nylon bio-based dipped gloves and cut-resistant bio-based dipped gloves were obtained respectively.
  • test data are as shown in the table below:

Abstract

本发明涉及一种浸胶手套用生物基浆料的制备方法以及采用该浆料制得的浸胶手套；采用本发明的生物基浆料生产的浸胶手套的耐磨、耐折性能更优良，手感更好，更有利于浸胶手套产品的商业推广应用。

Description

一种浸胶手套用生物基浆料的制备方法 技术领域
本发明涉及一种浸胶手套用生物基浆料的制备方法以及采用该浆料制得的浸胶手套，属于高分子材料技术领域。
 背景技术
PU涂层手套又称PU涂胶手套或PU浸胶手套、贴掌手套，手套是将经特殊处理的聚氨酯完全覆盖在手掌部分，能提供良好的防滑性能，并能防止人体手掌的手汗和微粒污染，普通的PU浸胶手套制作过程是高碳排放的，成品手套降解过程相对缓慢，对环境产生污染，随着材料科学的发展，人们尝试采用生物基聚氨酯材料来取代普通的PU材料，来制备浸胶手套用到的生物基浆料。常见的生物基材料是以谷物、豆科、秸秆、竹木 粉等可再生生物质通过生物转化获得生物高分子材料或单体，然后进一步聚合形成的环境友好的化工产品和绿色能源等高分子材料。
然而，目前现有的生物基浆料成分单一，采用生物基浆料制得的浸胶手套在弹性和泡孔大小等方面都会差一些，做成手套后会手感僵硬、背面渗胶、耐磨性、耐弯折性差。
 发明内容
本发明一方面提供了一种浸胶手套用生物基浆料的制备方法，其中，所述制备方法包括如下步骤：
S1.混合物A的制备：将120-180重量份DMF溶剂、2-10重量份仿蛋白助剂、0.2-2重量份氨基改性硅油和0.1-1重量份消泡剂混合并搅拌制得混合物A；
S2.混合物B的制备：向所述S1制得的混合物A中加入80-100重量份生物聚氨酯树脂，混合搅拌制得混合物B；
所述生物聚氨酯树脂的合成单体为生物基聚酯二元醇和生物基二苯基甲烷-4，4’-二异氰酸酯；所述生物聚酯二元醇为丁二酸与1，3丙二醇的聚合物；
S3.混合物C的制备：向所述S2制得的混合物B中加入0.5-1重量份耐磨耐刮剂，混合搅拌制得混合物C；
S4.混合物D的制备：向所述S3制得的混合物C中加入0.01-0.05重量份道康宁OFS-6040偶联剂，经过偶联作用制得混合物D；所述混合物D在常温下的粘度落入500-700厘泊的范围；
S5.混合物E的制备：向所述S4制得的混合物D中加入5-20重量份软质聚氨酯树脂，混合搅拌制得常温下粘度范围为800-1200厘泊的所述浸胶手套用生物基浆料；
所述软质聚氨酯树脂的合成单体为第一聚酯二元醇、第二聚酯二元醇和二苯基甲烷-4，4’-二异氰酸酯；
所述第一聚酯二元醇为聚己二酸、1，4丁二醇和乙二醇的聚合物，数均分子量为3000-5000g/mol；所述第二聚酯二元醇为聚己二酸与二乙二醇的聚合物，数均分子量为1500-2500g/mol；所述第一聚酯二元醇与所述第二聚酯二元醇的重量比为4~7：1。
优选的，所述软质聚氨酯树脂的配方包含以下重量份的组分：
第一聚酯二元醇                        18.5
第二聚酯二元醇                        3.5
二苯基甲烷-4，4’-二异氰酸酯           5.08
第一二醇扩链剂                        0.92
N,N’-二甲基甲酰胺                      70
泡孔调节剂                             2 ；
所述第一二醇扩链剂为乙二醇。
优选的，所述软质聚氨酯树脂的合成过程包括：
步骤a）：将所述第二聚酯二元醇，所述二醇扩链剂总质量的10%，所述N,N’-二甲基甲酰胺总质量的14.5%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的16%，升温至65-70℃，至反应物粘度达到250-300pa.s/50℃终止反应；
步骤b）：将所述第一聚酯二元醇，所述二醇扩链剂总质量的90%，所述N,N’-二甲基甲酰胺总质量的60%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的82%，升温至65-70℃，反应2-2.5小时；
步骤a）和步骤b）不分先后；
步骤c）：向所述步骤b）的产物中投入剩余的二苯基甲烷-4，4’-二异氰酸酯，直至反应物粘度达到300-350pa.s/50℃，加入剩余的N,N’-二甲基甲酰胺，终止反应后加入所述步骤a）的反应产物和所述泡孔调节剂得到所述软质聚氨酯树脂。
优选的，所述生物聚氨酯树脂的配方包含以下重量份的组分：
生物聚酯二元醇                        18.5
二苯基甲烷-4，4’-二异氰酸酯          9.52
第一二醇扩链剂                       1.32
第二二醇扩链剂                       0.66
N,N’-二甲基甲酰胺                     70；
所述第一二醇扩链剂为乙二醇；所述第二二醇扩链剂为1，4-丁二醇。
优选的，所述生物聚氨酯树脂的合成过程包括：
步骤I）将所述生物聚酯二元醇，所述N,N’-二甲基甲酰胺总质量的25%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的18%，升温至65-70℃，反应1-1.5小时；
步骤II）向步骤I）的产物中投入所述N,N’-二甲基甲酰胺总质量的45%、以及所述第一二醇扩链剂和所述第二二醇扩链剂，温度降至50-55℃，搅拌1小时后，在投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的70%，升温至70-75℃，反应2-2.5小时；再投入剩余的二苯基甲烷-4，4‘-二异氰酸酯，至反应物粘度达到350-400pa.s/50℃，再加入剩余的N,N’-二甲基甲酰胺，终止反应后得所述生物聚氨酯树脂。
优选的，所述仿蛋白助剂为氨基改性硅氧烷。
优选的，在所述S2中，采用7.5kw的高速搅拌机进行所述混合搅拌的操作，所述高速搅拌机的搅拌叶采用300mm直径的分散盘，其搅拌速度为800-1200转/分钟。
优选的，所述S3、S4和S5中的搅拌速度均落入400-700转/分钟。
本发明另一方面提供了一种浸胶手套，其中，所述浸胶手套所采用的浸胶浆料通过如上述的制备方法制得。
本发明提供了一种浸胶手套用生物基浆料的制备方法以及采用该浆料制得的浸胶手套；采用本发明的生物基浆料生产的浸胶手套的耐磨、耐折性能更优良，手感更好，更有利于浸胶手套产品的商业推广应用。
 实施方式
为使得本发明的发明目的、特征、优点能够更加的明显和易懂，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，下面所描述的实施例仅仅是本发明一部分实施例，而非全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
在本发明的描述中，需要理解的是，术语“上”、“下”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
实施例1
实施例1的浸胶手套用生物基浆料的配方如下（以重量份表示）：
生物聚氨酯树脂            90份
软质聚氨酯树脂            10份
DMF溶剂                   150份
仿蛋白助剂                 8份
氨基改性硅油               1份
消泡剂                      0.5份
道康宁OFS-6040偶联剂       0.03份
耐磨耐刮剂                  0.8份；
其中，
在本发明的一个具体实施方案中，所述生物聚氨酯树脂的合成单体为生物聚酯二元醇和二苯基甲烷-4，4’-二异氰酸酯；所述生物聚酯二元醇为丁二酸与1，3丙二醇的聚合物。
具体在本实施例中，生物聚氨酯树脂的配方包含以下重量份的组分：
生物聚酯二元醇                        18.5
二苯基甲烷-4，4’-二异氰酸酯          9.52
第一二醇扩链剂                       1.32
第二二醇扩链剂                       0.66
N,N’-二甲基甲酰胺                     70；
所述第一二醇扩链剂为乙二醇；所述第二二醇扩链剂为1，4-丁二醇。
具体在本实施例中，所述生物聚氨酯树脂的合成过程包括：
步骤I）将所述生物聚酯二元醇，所述N,N’-二甲基甲酰胺总质量的25%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的18%，升温至65-70℃，反应1-1.5小时；
步骤II）向步骤I）的产物中投入所述N,N’-二甲基甲酰胺总质量的45%、以及所述第一二醇扩链剂和所述第二二醇扩链剂，温度降至50-55℃，搅拌1小时后，在投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的70%，升温至70-75℃，反应2-2.5小时；再投入剩余的二苯基甲烷-4，4‘-二异氰酸酯，至反应物粘度达到350-400pa.s/50℃，再加入剩余的N,N’-二甲基甲酰胺，终止反应后得所述生物聚氨酯树脂。
在本发明的一个具体实施方案中，所述软质聚氨酯树脂的合成单体为第一聚酯二元醇、第二聚酯二元醇和二苯基甲烷-4，4’-二异氰酸酯；所述第一聚酯二元醇为聚己二酸、1，4丁二醇和乙二醇的聚合物，数均分子量为3000-5000g/mol；所述第二聚酯二元醇为聚己二酸与二乙二醇的聚合物，数均分子量为1500-2500g/mol；所述第一聚酯二元醇与所述第二聚酯二元醇的重量比为4~7：1。
具体在本实施例中，所述第一聚酯二元醇为聚己二酸、1，4丁二醇和乙二醇的聚合物，数均分子量约为4000g/mol；所述第二聚酯二元醇为聚己二酸与二乙二醇的聚合物，数均分子量为2000g/mol。
具体在本实施例中，所述软质聚氨酯树脂的配方包含以下重量份的组分：
第一聚酯二元醇                        18.5
第二聚酯二元醇                        3.5
二苯基甲烷-4，4’-二异氰酸酯           5.08
第一二醇扩链剂                        0.92
N,N’-二甲基甲酰胺                      70
泡孔调节剂                             2 ；
所述第一二醇扩链剂为乙二醇。
具体在本实施例中，所述软质聚氨酯树脂的合成过程包括：
步骤a）：将所述第二聚酯二元醇，所述二醇扩链剂总质量的10%，所述N,N’-二甲基甲酰胺总质量的14.5%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的16%，升温至65-70℃，至反应物粘度达到250-300pa.s/50℃终止反应；
步骤b）：将所述第一聚酯二元醇，所述二醇扩链剂总质量的90%，所述N,N’-二甲基甲酰胺总质量的60%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的82%，升温至65-70℃，反应2-2.5小时；
步骤a）和步骤b）不分先后；
步骤c）：向所述步骤b）的产物中投入剩余的二苯基甲烷-4，4’-二异氰酸酯，以及剩余的N,N’-二甲基甲酰胺，直至反应物粘度达到300-350pa.s/50℃，终止反应后加入所述步骤a）的反应产物和所述泡孔调节剂得到所述软质聚氨酯树脂。
具体在本实施例中，泡孔调节剂采用聚氨酯树脂的常规泡孔调节剂。
具体在本实施例中，仿蛋白助剂采用氨基改性硅氧烷。
具体在本实施例中，耐磨耐刮剂采用道康宁的DC3289产品。具体在本实施例中，消泡剂采用道康宁的DC57产品。
实施例1的浸胶手套用生物基浆料的制备方法，该制备方法包括如下步骤：
S1.混合物A的制备：将上述配方中的DMF溶剂、仿蛋白助剂、氨基改性硅油和消泡剂混合并搅拌制得混合物A；
具体在本实施例中，在搅拌桶（容量规格大约为1000-2000L）中，加入DMF溶剂、仿蛋白助剂、氨基改性硅油和消泡剂，在约1000转/分钟的高速搅拌条件下混合搅拌约30min；
S2.混合物B的制备：向S1制得的混合物A中加入上述的生物聚氨酯树脂，混合搅拌制得混合物B；
在本发明的一个优选实施方案中，在所述S2中，采用7.5kw的高速搅拌机进行所述混合搅拌的操作，所述高速搅拌机的搅拌叶采用300mm直径的分散盘，其搅拌速度为800-1200转/分钟。
具体在本实施例中，向S1制得的混合物A中加入上述的生物聚氨酯树脂，在约1000转/分钟的高速搅拌条件下，采用300mm直径的分散盘混合搅拌；搅拌的过程中，采用粘度测量仪器对混合物B的粘度进行监控测量（例如每隔5分钟测量），当混合物B的常温下粘度落入400-600厘泊时，停止搅拌。
S3.混合物C的制备：向S2制得的混合物B中加入上述的道康宁FBL-3289，混合搅拌制得混合物C；
道康宁FBL-3289是常规的脱模性手感剂，并且具有较佳的耐磨耐刮效果；本案的发明人尝试了多种手感剂，发现道康宁FBL-3289能够与生物聚氨酯树脂的融合性更好。
具体在本实施例中，S3的搅拌速度控制在约500转/分钟，同时将温度控制在20℃-40℃。
S4.混合物D的制备：向所述S3制得的混合物C中加入道康宁OFS-6040偶联剂，经过偶联作用制得混合物D；所述混合物D在常温下的粘度落入500-700厘泊的范围；
具体在本实施例中，加入催化剂后搅拌混匀，将搅拌速度控制在约500转/分钟，搅拌5min后停止搅动；然后，静止反应30min后得到混合物D。
S5.混合物E的制备：向S4制得的混合物D中加入软质聚氨酯树脂，混合搅拌制得常温下粘度范围为800-1200厘泊的所述浸胶手套用生物基浆料；
具体在本实施例中，加入蛋白聚氨酯树脂后，将搅拌速度控制在约500转/分钟，搅拌30min；搅拌过程中，采用粘度测量仪器对所得浆料的粘度进行监控测量（例如每隔5分钟测量），当浆料的粘度落入800-1200厘泊时，停止搅拌。
在本发明的一个优选实施方案中，若需要着色，则在最后获得的生物基浆料中加入着色浆。
应用例1：采用实施例1的生物基浆料的浸胶手套
应用例1的生物浸胶手套生产工艺包括如下步骤：
步骤一，手芯本体套模；将尼龙手套芯或防割手套芯分别套在手套模芯上；
步骤二，手芯套模后的浸胶，将步骤一中套模后的手芯浸入到实施例1的生物基浆料中，停留1-5秒；
步骤三，水洗工段，将浸胶后的手芯使用清洗水进行清洗；
步骤四，水洗后的烘干，使用烘箱，将水洗后的手芯进行烘干；
步骤五，脱模。
采用上述步骤，分别获得尼龙生物基浸胶手套和防割生物基浸胶手套。
（1）取市售的普通尼龙PU浸胶手套、与应用例1制得的尼龙生物基浸胶手套在同等环境下进行测试；测试数据如下表所示：
丛林测试前 普通尼龙PU浸胶手套 应用例1制得的尼龙生物基浸胶手套
耐磨（转） 8000 8000
耐折（次） 90000 90000
手套厚度（mm） 0.8 0.76
胶厚度（mm） 0.18 0.15
丛林测试后（一周） 普通尼龙PU浸胶手套 应用例1制得的尼龙生物基浸胶手套
耐磨（转） 6000 6000
耐折（次） 50000 50000
（2）取市售的普通防割PU浸胶手套、与应用例1制得的防割生物基浸胶手套在同等环境下进行测试；测试数据如下表所示：
丛林测试前 普通防割PU浸胶手套 应用例1制得的防割生物基浸胶手套
耐磨（转） 10000 10000
耐折（次） 90000 90000
手套厚度（mm） 1.46 1.45
胶厚度（mm） 0.08 0.07
丛林测试后（一周） 普通防割PU浸胶手套 应用例1制得的防割生物基浸胶手套
耐磨（转） 8000 8000
耐折（次） 50000 50000
综合以上实验数据可以看出，采用实施例1浸胶浆料制作的尼龙浸胶手套的耐磨、耐折性能相较于普通的PU浸胶手套得到大大的提升，同时，制作的浸胶手套的浸胶涂层相较于普通的PU浸胶手套更薄，改善了使用手感，更有利于浸胶手套产品的商业推广应用。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的得同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
以上所述，以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (9)

  1. 一种浸胶手套用生物基浆料的制备方法，其特征在于：所述制备方法包括如下步骤：
    S1.混合物A的制备：将120-180重量份DMF溶剂、2-10重量份仿蛋白助剂、0.2-2重量份氨基改性硅油和0.1-1重量份消泡剂混合并搅拌制得混合物A；
    S2.混合物B的制备：向所述S1制得的混合物A中加入80-100重量份生物聚氨酯树脂，混合搅拌制得混合物B；
    所述生物聚氨酯树脂的合成单体为生物基聚酯二元醇和生物基二苯基甲烷-4，4’-二异氰酸酯；所述生物聚酯二元醇为丁二酸与1，3丙二醇的聚合物；
    S3.混合物C的制备：向所述S2制得的混合物B中加入0.5-1重量份耐磨耐刮剂，混合搅拌制得混合物C；
    S4.混合物D的制备：向所述S3制得的混合物C中加入0.01-0.05重量份道康宁OFS-6040偶联剂，经过偶联作用制得混合物D；所述混合物D在常温下的粘度落入500-700厘泊的范围；
    S5.混合物E的制备：向所述S4制得的混合物D中加入5-20重量份软质聚氨酯树脂，混合搅拌制得常温下粘度范围为800-1200厘泊的所述浸胶手套用生物基浆料；
    所述软质聚氨酯树脂的合成单体为第一聚酯二元醇、第二聚酯二元醇和二苯基甲烷-4，4’-二异氰酸酯；
    所述第一聚酯二元醇为聚己二酸、1，4丁二醇和乙二醇的聚合物，数均分子量为3000-5000g/mol；所述第二聚酯二元醇为聚己二酸与二乙二醇的聚合物，数均分子量为1500-2500g/mol；所述第一聚酯二元醇与所述第二聚酯二元醇的重量比为4~7：1。
  2. 如权利要求1所述的制备方法，其特征在于：
    所述软质聚氨酯树脂的配方包含以下重量份的组分：
    第一聚酯二元醇                        18.5
    第二聚酯二元醇                        3.5
    二苯基甲烷-4，4’-二异氰酸酯           5.08
    第一二醇扩链剂                        0.92
    N,N’-二甲基甲酰胺                      70
    泡孔调节剂                             2 ；
    所述第一二醇扩链剂为乙二醇。
  3. 如权利要求2所述的制备方法，其特征在于：
    所述软质聚氨酯树脂的合成过程包括：
    步骤a）：将所述第二聚酯二元醇，所述二醇扩链剂总质量的10%，所述N,N’-二甲基甲酰胺总质量的14.5%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的16%，升温至65-70℃，至反应物粘度达到250-300pa.s/50℃终止反应；
    步骤b）：将所述第一聚酯二元醇，所述二醇扩链剂总质量的90%，所述N,N’-二甲基甲酰胺总质量的60%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的82%，升温至65-70℃，反应2-2.5小时；
    步骤a）和步骤b）不分先后；
    步骤c）：向所述步骤b）的产物中投入剩余的二苯基甲烷-4，4’-二异氰酸酯，直至反应物粘度达到300-350pa.s/50℃，加入剩余的N,N’-二甲基甲酰胺，终止反应后加入所述步骤a）的反应产物和所述泡孔调节剂得到所述软质聚氨酯树脂。
  4. 如权利要求1所述的制备方法，其特征在于：
    所述生物聚氨酯树脂的配方包含以下重量份的组分：
    生物聚酯二元醇                        18.5
    二苯基甲烷-4，4’-二异氰酸酯          9.52
    第一二醇扩链剂                       1.32
    第二二醇扩链剂                       0.66
    N,N’-二甲基甲酰胺                     70；
    所述第一二醇扩链剂为乙二醇；所述第二二醇扩链剂为1，4-丁二醇。
  5. 如权利要求4所述的制备方法，其特征在于：
    所述生物聚氨酯树脂的合成过程包括：
    步骤I）将所述生物聚酯二元醇，所述N,N’-二甲基甲酰胺总质量的25%投入反应釜混合均匀，升温至40-45℃，再投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的18%，升温至65-70℃，反应1-1.5小时；
    步骤II）向步骤I）的产物中投入所述N,N’-二甲基甲酰胺总质量的45%、以及所述第一二醇扩链剂和所述第二二醇扩链剂，温度降至50-55℃，搅拌1小时后，在投入所述二苯基甲烷-4，4’-二异氰酸酯总质量的70%，升温至70-75℃，反应2-2.5小时；再投入剩余的二苯基甲烷-4，4‘-二异氰酸酯，至反应物粘度达到350-400pa.s/50℃，再加入剩余的N,N’-二甲基甲酰胺，终止反应后得所述生物聚氨酯树脂。
  6. 根据权利要求1至5中任意一项所述的制备方法，其特征在于：所述仿蛋白助剂为氨基改性硅氧烷。
  7. 根据权利要求1至5中任意一项所述的制备方法，其特征在于：在所述S2中，采用7.5kw的高速搅拌机进行所述混合搅拌的操作，所述高速搅拌机的搅拌叶采用300mm直径的分散盘，其搅拌速度为800-1200转/分钟。
  8. 根据权利要求7所述的制备方法，其特征在于：所述S3、S4和S5中的搅拌速度均落入400-700转/分钟。
  9. 一种浸胶手套，其特征在于：所述浸胶手套所采用的浸胶浆料通过如权利要求1至8中任意一项所述的制备方法制得。
PCT/CN2023/078426 2022-07-18 2023-02-27 一种浸胶手套用生物基浆料的制备方法 WO2024016667A1 (zh)

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