WO2020024538A1 - 高透高弹聚氨酯弹性体的制备方法 - Google Patents

高透高弹聚氨酯弹性体的制备方法 Download PDF

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WO2020024538A1
WO2020024538A1 PCT/CN2018/122976 CN2018122976W WO2020024538A1 WO 2020024538 A1 WO2020024538 A1 WO 2020024538A1 CN 2018122976 W CN2018122976 W CN 2018122976W WO 2020024538 A1 WO2020024538 A1 WO 2020024538A1
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isocyanate
polyurethane elastomer
ptmg
component
polyurethane
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PCT/CN2018/122976
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English (en)
French (fr)
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刘兆阳
宿金明
房玉俊
李涛
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山东一诺威聚氨酯股份有限公司
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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
    • C08G18/28—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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings

Definitions

  • the invention relates to a method for preparing a high-permeability and high-elastic polyurethane elastomer, and belongs to the technical field of polyurethane application.
  • Polyurethane is a polymer synthetic material with properties between rubber and plastic. It is characterized by a wide range of hardness adjustment. It has both the elasticity of rubber and the hardness of plastic. It has good mechanical properties, wear resistance and resilience. It has become the fastest growing polymer material after PE, PP, PVC, PS, and phenolic resin.
  • the transparent polyurethane elastomer not only has excellent optical properties, but also has a wide range of hardness and high mechanical strength. It is suitable for optics, ballistic launch, and crafts making. It can be used to make spectacle lenses, bulletproof glass, and trademark nameplates. Wait.
  • the type of isocyanate, the type of chain extender, the type and molecular weight of the polyol will all affect the mechanical properties and optical stability of the polyurethane elastomer.
  • Elastomers synthesized from polyester polyols contain highly polar ester groups, which are prone to crystallization and affect the transparency of polyurethane elastomers.
  • the polyether polyols have weak interactions, low crystallinity, and it is easier to produce highly transparent polyurethane elastomers.
  • propylene oxide polyether (PPG) has the advantages of low price, low viscosity at room temperature, and easy to use.
  • PPG propylene oxide polyether
  • the elastomer produced by using it has poor rebound and mechanical properties need to be improved.
  • CN101134843A discloses a method for preparing high-elastic polyurethane elastomer, which uses PTMG2000 or PPG3000 mixed with BDO, catalyst, and anti-aging agent as the polymer component, and the isocyanate in the prepolymer component is selected by MDI and carbodiimide modification MDI and their mixtures have a narrow hardness range (Shore A80 ⁇ 2) and poor rebound performance.
  • the isocyanates commonly used in the synthesis of polyurethane elastomers are mainly aromatic diisocyanates TDI and MDI. Due to the presence of benzene rings, polyurethane elastomers synthesized using these two isocyanates contain bridges of aromatic urea. Once exposed to ultraviolet light, they are easily generated. The color-developed quinone structure makes the product yellow and reduces the transparency. In order to solve the above problems, a method for preparing a high-permeability and high-elastic polyurethane elastomer was explored.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for preparing a high-permeability and high-elastic polyurethane elastomer.
  • the high-permeability and high-elasticity polyurethane elastomer prepared by this method not only has a wide range of hardness, but also has high transparency and resilience, and has yellowing resistance characteristics, which meets the market demand for high-permeability and high-elasticity polyurethane elastomers. .
  • the method for preparing the high-permeability and high-elastic polyurethane elastomer according to the present invention specifically includes the following steps:
  • PTMG, HDO, catalyst and antioxidant are mixed under a certain mass ratio at room temperature and sealed and stored;
  • PTMG reacts with isocyanate at 80 to 85 ° C for 2 to 3 hours, the degree of vacuum for removing bubbles is ⁇ -0.095 MPa, and a polyurethane prepolymer component having an isocyanate content of 8.5 to 13.2% is prepared;
  • the mixing temperature of the polymer component and the polyurethane prepolymer component is controlled at 60 to 80 ° C, and the polymer component and the polyurethane prepolymer component are mixed uniformly at a ratio of 40 to 100: 100, and then poured into 70 to 90 In the mold at °C, the mold is opened for 30 to 45 minutes without vulcanization, and a highly transparent and highly elastic polyurethane elastomer is obtained.
  • the molecular weight of PTMG in step (1) and step (2) is 1000-2000, the moisture content of PTMG is ⁇ 0.03%, PTMG is one or two of PTMG1000 or PTMG2000; the catalyst is an organic bismuth catalyst.
  • the polymer component described in step (1) is composed of PTMG, HDO, catalyst and antioxidant. Based on mass fraction, PTMG1000 is 0 to 62.5%, PTMG2000 is 0 to 93%, HDO is 6 to 38.3%, and catalyst is 0.4 to 0.7% and antioxidant 0.5%; the above mass fractions refer to the mass of the polymer component.
  • Polyurethane prepolymer components include PTMG and isocyanate; PTMG is one or both of PTMG1000 or PTMG2000.
  • PTMG1000 accounts for 0 to 10.7 wt% of the polyurethane prepolymer component
  • PTMG2000 accounts for 43 to 66.4 wt% of the polyurethane prepolymer component.
  • Isocyanate is an aromatic isocyanate or a mixture of an aromatic isocyanate and an aliphatic isocyanate, the aromatic isocyanate is MDI-100, the aliphatic isocyanate is one or two of H 12 MDI or IPDI, and the aliphatic isocyanate accounts for the total amount of isocyanate 0 to 20%.
  • aliphatic isocyanate H 12 MDI accounts for 0 to 4.3% of the polyurethane prepolymer component
  • IPDI accounts for 0 to 9.3% of the polyurethane prepolymer component
  • aromatic isocyanate MDI-100 accounts for the polyurethane prepolymer group. 33.6 to 38.7% of points.
  • the hardness of the polyurethane elastomer is 65 ⁇ 95; the rebound is 75-85%; the light transmittance is ⁇ 89% and the highest is 96%; the haze is ⁇ 1.1% and the lowest is 0.6%.
  • the method for preparing the high-permeability and high-elastic polyurethane elastomer according to the present invention specifically includes the following steps:
  • the present invention adopts a two-component system.
  • the two-component composite material includes a polymer component and a prepolymer component, which are respectively named as component A and component B.
  • the content percentages involved are all weight percentages.
  • the preparation method of component A is as follows: a mixture prepared by mixing PTMG, HDO, a catalyst and an antioxidant in terms of weight percentage, at room temperature PTMG1000 0 to 62.5% or PTMG2000 0 to 93% and HDO 6 to 38.3 % And catalyst 0.4-0.7% and anti-oxidant 0.5% are mixed evenly and sealed.
  • the type and proportion of the polyether polyol can be reasonably adjusted within the above range according to the performance of the desired product; the content of the catalyst can be selected within the above range according to the needs of the actual reaction.
  • the preparation method of component B is as follows: a prepolymer, in terms of weight percentage, PTMG and isocyanate are reacted at 80-85 ° C for 2 to 3 hours, the moisture content of PTMG is preferably ⁇ 0.03%, and PTMG1000 0 to 10.7 %, PTMG2000 43 ⁇ 66.4%, isocyanate can choose MDI-100 33.6 ⁇ 38.7%, H 12 MDI 0 ⁇ 4.3%, IPDI 0 ⁇ 9.3%, the vacuum degree of removing bubbles is preferably ⁇ -0.095MPa to obtain prepolymer The isocyanate content is 8.5 to 13.2%.
  • the mixing temperature of the polymer component and the polyurethane prepolymer component is controlled at 60 to 80 ° C, and the polymer component and the polyurethane prepolymer component are mixed uniformly at a ratio of 40 to 100: 100, and then poured into 70 to 90 In the mold at °C, the mold is opened for 30 to 45 minutes without vulcanization, and a highly transparent and highly elastic polyurethane elastomer is obtained.
  • this patent first increases the length of the chain extender, uses HDO with a longer molecular chain as the chain extender, and reduces the molecular weight of the polyether polyol (number average molecular weight 1000) The length of the soft segment chain is shortened, preventing the formation of perfect crystals.
  • the aliphatic diisocyanate H 12 MDI and IPDI without benzene ring are introduced as isocyanates to avoid yellowing of the product.
  • this patent uses polytetramethylene ether glycol (PTMG) as the polyol and is added to the formulation of the product with low hardness A certain proportion of PTMG2000 to improve the rebound of the product. Therefore, a method for preparing a high-permeability and high-elastic polyurethane elastomer is provided, and the method can be used for preparing high-hardness large-sized products.
  • PTMG polytetramethylene ether glycol
  • the present invention has the following beneficial effects:
  • the high-permeability and high-elasticity polyurethane elastomer prepared by this method has high transparency and resilience, and has yellowing resistance characteristics, which can meet the market demand for high-permeability and high-elasticity polyurethane elastomers.
  • the method for preparing a high-permeability and high-elastic polyurethane elastomer has the advantages of simple operation, excellent processing performance, energy saving, and low equipment requirements.
  • the hardness of the polyurethane elastomer prepared by this method is 65 to 95; rebound is 75 to 85%; light transmittance is ⁇ 89% and the highest is 96%; haze is ⁇ 1.1% and the lowest is 0.6%.
  • the components of the two-component high-permeability and high-elastic polyurethane elastomer are as follows:
  • Component A 93% and 7% of PTMG2000 and HDO with moisture content ⁇ 0.03%, 0.4% of bismuth catalyst, 0.2% of UV-1076 and 0.3% of UV-328, respectively, and mixed to obtain component A.
  • Component B PTMG2000 66.4% and MDI-100 33.6% with moisture content ⁇ 0.03% are reacted at 85 ° C. for 2.5 hours, and air bubbles are removed under vacuum (-0.095MPa) to obtain a prepolymer having an isocyanate content of 8.5%.
  • the components of the two-component high-permeability and high-elastic polyurethane elastomer are as follows:
  • Component A PTMG1000 with moisture content ⁇ 0.03%, PTMG2000 and HDO 25%, 65%, and 10% each, bismuth catalyst 0.5%, antioxidants UV-1076 0.2% and UV-328 0.3%, mixed evenly to get A Components.
  • Component B PTMG2000 63% and MDI-100 37% with moisture content ⁇ 0.03% are reacted at 85 ° C. for 2.5 hours, and bubbles are removed under vacuum (-0.095 MPa) to obtain a prepolymer having an isocyanate content of 9.8%.
  • the components of the two-component high-permeability and high-elastic polyurethane elastomer are as follows:
  • Component A PTMG1000 with moisture content ⁇ 0.03%, 41.7%, 38.3%, and 20% of PTMG2000 and HDO, 0.6% of bismuth catalyst, 0.2% of UV-1076 antioxidant and 0.3% of UV-328, mixed to obtain A. Components.
  • Component B PTMG2000 57% with moisture content ⁇ 0.03%, MDI-100 38.7%, H 12 MDI 4.3%, react at 85 ° C for 2 hours, remove bubbles in vacuum (-0.095MPa), and get 12% isocyanate content Prepolymer.
  • the components of the two-component high-permeability and high-elastic polyurethane elastomer are as follows:
  • Component A 62.5% and 37.5% of PTMG1000 and HDO with moisture content ⁇ 0.03%, 0.7% of bismuth catalyst, 0.2% of UV-1076 antioxidant and 0.3% of UV-328, respectively, and mixed to obtain component A.
  • Component B PTMG1000 10.7% with moisture content ⁇ 0.03%, PTMG2000 43% and MDI-100 37%, IPDI 9.3% react at 85 ° C for 2 hours, remove the air bubbles under vacuum (-0.095MPa), and obtain isocyanate content It was a 13.2% prepolymer.
  • Component A PTMG2000 and BDO with moisture content ⁇ 0.03%, 86.4% and 13.6% each, bismuth catalyst 0.6%, antioxidants UV-1076 and UV-328 0.2% and 0.3%, respectively, and mixed to obtain component A.
  • Component B PTMG2000 57% with moisture content ⁇ 0.03%, MDI-100 38.7%, H 12 MDI 4.3%, react at 85 ° C for 2 hours, remove bubbles in vacuum (-0.095MPa), and get 12% isocyanate content Prepolymer.
  • the polyurethane elastomers prepared in Examples 1-4 and Comparative Example 1 were tested for performance.
  • the transmittance and haze of the products were measured by Guangzhou Packaging Equipment Co., Ltd. SGW-810 haze transmittance meter.
  • the test conditions were as follows: After preheating for 20 minutes, at room temperature, place a sample sheet with a thickness of 2 mm into the colorimeter and fix it with a positioning clip so that it is close to the colorimeter seat wall. Push into the light path to measure the visible light transmittance of the sample.
  • the performance test results of Examples 1-4 and Comparative Example 1 are shown in Table 1.
  • Example 1 Example 2
  • Example 3 Example 4 Comparative Example 1 Hardness (23 °C) / Shore A 65 75 85
  • 90 85 Tensile strength / MPa 11 16 20 25 13 Tear strength / (KN / m) 50 55 59 64 53 Rebound (23 °C) /% 85 82 79 75 70 Transmittance/% 89 90 92 96 85
  • Table 1 is a table showing the performance test results of the polyurethane elastomers obtained in Examples 1-4 of the present invention and Comparative Example 1. It can be seen from comparison with Comparative Example 1 that the present invention uses a polymer component containing 1,6-hexanediol.
  • the prepared polyurethane elastomer has a significant improvement in transparency, a significant increase in light transmittance, and a decrease in haze.
  • the elasticity of the product of Example 3 is higher when the elastomer hardness is the same.
  • the proportion of HDO increases, the light transmittance of the elastomer also increases.

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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)

Abstract

高透高弹聚氨酯弹性体的制备方法，属于聚氨酯应用技术领域。PTMG、HDO、催化剂和抗氧化剂在室温条件下，按照一定质量比混合均匀后密封保存；PTMG与异氰酸酯在80～85℃下反应2～3小时，真空度≧-0.095MPa，得到异氰酸根含量为8.5～13.2％的聚氨酯预聚物组分；将聚合物组分和聚氨酯预聚物组分控制在60～80℃混合，聚合物组分与聚氨酯预聚物组分按40～100:100的比例混合均匀后，浇注入70～90℃的模具中，30～45分钟开模，得到高透高弹聚氨酯弹性体。采用该方法制备的高透高弹聚氨酯弹性体具有较高的透明性、回弹性和耐黄变特性，满足市场对高透高弹聚氨酯弹性体的需求。

Description

高透高弹聚氨酯弹性体的制备方法 技术领域
本发明涉及一种高透高弹聚氨酯弹性体的制备方法，属于聚氨酯应用技术领域。
背景技术
聚氨酯是一种性能介于橡胶与塑料之间的高分子合成材料，其特点是硬度调整范围宽，既有橡胶的弹性又有塑料的硬度，具有良好的机械性能、耐磨性能和回弹性能，成为了继PE、PP、PVC、PS、酚醛树脂后发展最为迅速的高分子材料。而透明聚氨酯弹性体不仅具有优异的光学性能，同时又具有聚氨酯弹性很宽的硬度范围和较高的机械强度，适用于光学、弹道发射和工艺品制作等，可制作眼镜片、防弹玻璃、商标铭牌等。异氰酸酯的种类、扩链剂的种类、多元醇的种类及分子量等都会影响到聚氨酯弹性体的力学性能以及光学稳定性。
用聚酯多元醇合成的弹性体含有极性高的酯基，易产生结晶，影响聚氨酯弹性体的透明性。而聚醚多元醇分子间的相互作用弱，制品结晶度低，更易制得高透明性的聚氨酯弹性体。环氧丙烷聚醚(PPG)作为最常见的聚醚多元醇，具有价格低及室温下粘度小，使用方便的优势，但使用其制作的弹性体回弹差、力学性能有待提高。
CN101134843A公开了一种高弹聚氨酯弹性体的制备方法，采用PTMG2000或PPG3000与BDO、催化剂、抗老化剂混合作为聚合物组分，预聚物组分中的异氰酸酯选择MDI、碳化二亚胺改性的MDI以及它们的混合物，制作的高弹弹性体硬度范围窄(邵A80±2)、回弹性能差。
合成聚氨酯弹性体常用的异氰酸酯主要为芳香族二异氰酸酯TDI和MDI，由于苯环的存在导致采用这两种异氰酸酯合成的聚氨酯弹性体含有芳香族脲的桥键，一旦经紫外光照射，极易生成显色的醌式结构，从而使制品变黄，透明性降低。为解决上述问题，探究一种制备高透高弹聚氨酯弹性体的方法。
发明内容
本发明的目的是克服现有技术的不足，提供一种高透高弹聚氨酯弹性体的制备方法。采用该方法制备的高透高弹聚氨酯弹性体不仅具有较宽的硬度范围，而且具有较高的透明性和回弹性，并具有耐黄变特性，满足市场对高透高弹聚氨酯弹性体的需求。
本发明所述的高透高弹聚氨酯弹性体的制备方法，具体包括以下步骤：
(1)聚合物组分的制备
PTMG、HDO、催化剂和抗氧化剂在室温条件下，按照一定质量比混合均匀后密封保存；
(2)聚氨酯预聚物组分的制备
PTMG与异氰酸酯在80～85℃下反应2～3小时，脱除气泡的真空度≧-0.095MPa，制备得到异氰酸根含量为8.5～13.2％的聚氨酯预聚物组分；
(3)聚氨酯弹性体的制备
将聚合物组分和聚氨酯预聚物组分的混合温度控制在60～80℃，聚合物组分与聚氨酯预聚物组分按40～100:100的比例混合均匀后，浇注入70～90℃的模具中，30～45分钟开模，无需硫化，得到高透高弹聚氨酯弹性体。
其中：
步骤(1)和步骤(2)中的PTMG分子量为1000-2000，PTMG水分含量≦0.03％，PTMG是PTMG1000或PTMG2000中的一种或两种；催化剂为有机铋类催化剂。
步骤(1)中所述的聚合物组分由PTMG、HDO、催化剂和抗氧剂组成，以质量分数计，PTMG1000 0～62.5％、PTMG2000 0～93％、HDO 6～38.3％、催化剂0.4～0.7％和抗氧剂0.5％；以上质量分数均是指占聚合物组分的质量。
聚氨酯预聚物组分包括PTMG和异氰酸酯；PTMG是PTMG1000或PTMG2000中的一种或两种。
PTMG1000占聚氨酯预聚物组分的0～10.7wt％，PTMG2000占聚氨酯预聚物组分的43～66.4wt％。
异氰酸酯为芳香族异氰酸酯或芳香族异氰酸酯与脂肪族异氰酸酯的混合物，芳香族异氰酸酯为MDI-100，脂肪族异氰酸酯为H 12MDI或IPDI中的一种或两种，且脂肪族异氰酸酯占异氰酸酯总量的0～20％。
以质量分数计，脂肪族异氰酸酯H 12MDI占聚氨酯预聚物组分的0～4.3％、IPDI占聚氨酯预聚物组分的0～9.3％；芳香族异氰酸酯MDI-100占聚氨酯预聚物组分的33.6～38.7％。
聚氨酯弹性体的硬度邵A 65～95；回弹75～85％；透光率≧89％，最高达96％；雾度≦1.1％，最低达0.6％。
作为一个优选的技术方案，本发明所述的高透高弹聚氨酯弹性体的制备方法，具体包括以下步骤：
本发明采用双组分体系，双组分组合料包括聚合物组分与预聚物组分，分别命名为A组分和B组分，所涉及到的含量百分数皆为重量百分数。
(1)A组分的制备方法如下：一种混合物，以重量百分数计，PTMG、HDO、催化剂和抗氧化剂混合制得，室温下PTMG1000 0～62.5％或PTMG2000 0～93％与HDO 6～38.3％和催化剂0.4～0.7％和抗氧剂0.5％混合均匀后密封保存。
所述聚醚多元醇的种类和所占份数可根据所需产品的性能在上述范围内进行合理地调 整；所述催化剂的含量可根据实际反应的需要在上述范围内进行选取。
(2)B组分的制备方法如下：一种预聚物，以重量百分数计，PTMG与异氰酸酯在80～85℃下反应2～3小时，PTMG水分含量优选为≦0.03％，PTMG1000 0～10.7％，PTMG2000 43～66.4％，异氰酸酯可选择MDI-100 33.6～38.7％，H 12MDI 0～4.3％，IPDI 0～9.3％，脱除气泡的真空度优选为≧-0.095MPa，得到预聚体的异氰酸根含量为8.5～13.2％。
(3)聚氨酯弹性体的制备
将聚合物组分和聚氨酯预聚物组分的混合温度控制在60～80℃，聚合物组分与聚氨酯预聚物组分按40～100:100的比例混合均匀后，浇注入70～90℃的模具中，30～45分钟开模，无需硫化，得到高透高弹聚氨酯弹性体。
本发明中提高聚氨酯弹性体的透明性，本专利首先增加扩链剂的链段长度，采用分子链更长的HDO作为扩链剂，并降低聚醚多元醇的分子量(数均分子量1000)，使软段链长度变短，阻碍形成完善结晶，另外，引入不含苯环的脂肪族二异氰酸酯H 12MDI以及IPDI作为异氰酸酯，避免制品变黄。考虑到在提高制品透明性的同时不损失其力学性能，使制品拥有高弹的特性，本专利采用聚四亚甲基醚二醇(PTMG)作为多元醇，并在硬度低的制品配方中加入一定比例的PTMG2000，以提高制品的回弹。从而提供一种高透高弹聚氨酯弹性体的制备方法，并可以用于制备高硬度大件制品。
本发明与现有技术相比，具有以下有益效果：
(1)采用该方法制备的高透高弹聚氨酯弹性体具有较高的透明性和回弹性，并具有耐黄变特性，可满足市场对高透高弹聚氨酯弹性体的需求。
(2)该制备高透高弹聚氨酯弹性体的方法具有操作简单、加工工艺性能优良、节省能源、对设备要求低等优点。
(3)采用该方法制备得到的聚氨酯弹性体的硬度邵A 65～95；回弹75～85％；透光率≧89％，最高达96％；雾度≦1.1％，最低达0.6％。
具体实施方式
以下结合实施例对本发明作进一步描述。
Figure PCTCN2018122976-appb-000001
Figure PCTCN2018122976-appb-000002
实施例1
双组分高透高弹聚氨酯弹性体的组分如下：
A组分：水分含量≦0.03％的PTMG2000和HDO各93％和7％，铋类催化剂0.4％，抗氧剂UV-1076 0.2％和UV-328 0.3％，混合均匀得到A组分。
B组分：水分含量≦0.03％的PTMG2000 66.4％和MDI-100 33.6％在85℃反应2.5小时，真空(-0.095MPa)脱除气泡，得到异氰酸根含量为8.5％的预聚体。
A、B双组分的混合温度控制在65℃，按照A：B＝100：100的质量比例混合均匀后，浇注入75℃的模具中，40分钟开模，可得到硬度为邵氏65A，回弹为85％的高透高弹聚氨酯弹性体。
实施例2
双组分高透高弹聚氨酯弹性体的组分如下：
A组分：水分含量≦0.03％的PTMG1000，PTMG2000和HDO各25％、65％和10％，铋类催化剂0.5％，抗氧剂UV-1076 0.2％和UV-328 0.3％，混合均匀得到A组分。
B组分：水分含量≦0.03％的PTMG2000 63％和MDI-100 37％在85℃反应2.5小时，真空(-0.095MPa)脱除气泡，得到异氰酸根含量为9.8％的预聚体。
A、B双组分的混合温度控制在65℃，按照A：B＝80：100的质量比例混合均匀后，浇注入75℃的模具中，40分钟开模，可得到硬度为邵氏75A，回弹为82％的高透高弹聚氨酯弹性体。
实施例3
双组分高透高弹聚氨酯弹性体的组分如下：
A组分：水分含量≦0.03％的PTMG1000，PTMG2000和HDO各41.7％、38.3％和20％，铋类催化剂0.6％，抗氧剂UV-1076 0.2％和UV-328 0.3％，混合均匀得到A组分。
B组分：水分含量≦0.03％的PTMG2000 57％和MDI-100 38.7％，H 12MDI 4.3％在85℃反应2小时，真空(-0.095MPa)脱除气泡，得到异氰酸根含量为12％的预聚体。
A、B双组分的混合温度控制在65℃，按照A：B＝60：100的质量比例混合均匀后，浇注入75℃的模具中，40分钟开模，可得到硬度为邵氏85A，回弹为79％的高透高弹聚氨酯弹性体。
实施例4
双组分高透高弹聚氨酯弹性体的组分如下：
A组分：水分含量≦0.03％的PTMG1000和HDO各62.5％和37.5％，铋类催化剂0.7％，抗氧剂UV-1076 0.2％和UV-328 0.3％，混合均匀得到A组分。
B组分：水分含量≦0.03％的PTMG1000 10.7％，PTMG2000 43％和MDI-100 37％，IPDI9.3％在85℃反应2小时，真空(-0.095MPa)脱除气泡，得到异氰酸根含量为13.2％的预聚体。
A、B双组分的混合温度控制在65℃，按照A：B＝40：100的质量比例混合均匀后，浇注入75℃的模具中，40分钟开模，可得到硬度为邵氏90A，回弹为75％的高透高弹聚氨酯弹性体。
对比例1
A组分：水分含量≦0.03％的PTMG2000和BDO各86.4％和13.6％，铋类催化剂0.6％，抗氧剂UV-1076和UV-328各0.2％和0.3％，混合均匀得到A组分。
B组分：水分含量≦0.03％的PTMG2000 57％和MDI-100 38.7％，H 12MDI 4.3％在85℃反应2小时，真空(-0.095MPa)脱除气泡，得到异氰酸根含量为12％的预聚体。
A、B双组分的混合温度控制在65℃，按照A：B＝60：100的质量比例混合均匀后，浇注入75℃的模具中，40分钟开模，可得到硬度为邵氏85A，回弹为70％的高透高弹聚氨酯弹性体。
对实施例1-4和对比例1制备的聚氨酯弹性体进行性能检测，制品的透光率及雾度采用广州包装设备有限公司SGW-810型雾度透光率仪，测试条件为：机器开机预热20min后，室温下，将厚度为2mm的试样薄片放入比色器内用定位夹固定，使其紧靠比色器座壁，连续多次较正仪器后，将待测试样推入光路，即可测得试样可见光透过率。实施例1-4和对比例1的性能测试结果见表1。
表1实施例1-4和对比例1的性能测试结果
项目 实施例1 实施例2 实施例3 实施例4 对比例1
硬度(23℃)/邵A 65 75 85 90 85
拉伸强度/MPa 11 16 20 25 13
撕裂强度/(KN/m) 50 55 59 64 53
回弹(23℃)/％ 85 82 79 75 70
透光率/％ 89 90 92 96 85
雾度/％ 1.0 0.8 0.7 0.6 1.5
表1为本发明实施例1-4与对比例1所获得的聚氨酯弹性体的性能测试结果表，与对比例1进行对比可知，本发明采用含1，6-己二醇的聚合物组分制备获得的聚氨酯弹性体，其透明性有显著的提高，透光率增加明显，雾度亦有所降低。对比实施例3和对比例1，当弹性体硬度相同时实施例3制品的回弹率更高。并且在实施例1-4中随着HDO所占比例的增加，弹性体的透光率也随之增加。随着聚合物组分中PTMG1000比例的降低、PTMG2000比例的增加，高透聚氨酯弹性体的回弹率有明显的提升，这主要是由于多元醇分子量的增加使软链段比例增加，分子链柔韧性增加。

Claims (8)

  1. 一种高透高弹聚氨酯弹性体的制备方法，其特征在于：具体包括以下步骤：
    (1)聚合物组分的制备
    PTMG、HDO与催化剂和抗氧剂在室温条件下，按照一定质量比混合均匀后密封保存；
    (2)聚氨酯预聚物组分的制备
    PTMG与异氰酸酯在80～85℃下反应2～3小时，脱除气泡的真空度≧-0.095MPa，制备得到异氰酸根含量为8.5～13.2％的聚氨酯预聚物组分；
    (3)聚氨酯弹性体的制备
    将聚合物组分和聚氨酯预聚物组分的混合温度控制在60～80℃，聚合物组分与聚氨酯预聚物组分按40～100:100的比例混合均匀后，浇注入70～90℃的模具中，30～45分钟开模，无需硫化，得到高透高弹聚氨酯弹性体。
  2. 根据权利要求1所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：步骤(1)和步骤(2)中的PTMG分子量为1000-2000，PTMG水分含量≦0.03％，PTMG是PTMG1000或PTMG2000中的一种或两种；催化剂为有机铋类催化剂；抗氧剂是UV-328和UV-1076的混合物。
  3. 根据权利要求1所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：步骤(1)中所述的聚合物组分由PTMG、HDO、催化剂和抗氧剂组成，以质量分数计，PTMG1000 0～62.5％、PTMG2000 0～93％、HDO 6～38.3％、催化剂0.4～0.7％和抗氧剂0.5％。
  4. 根据权利要求1所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：聚氨酯预聚物组分包括PTMG和异氰酸酯；PTMG是PTMG1000或PTMG2000中的一种或两种。
  5. 根据权利要求4所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：PTMG1000占聚氨酯预聚物组分的0～10.7wt％，PTMG2000占聚氨酯预聚物组分的43～66.4wt％。
  6. 根据权利要求4所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：异氰酸酯为芳香族异氰酸酯或芳香族异氰酸酯与脂肪族异氰酸酯的混合物，芳香族异氰酸酯为MDI-100，脂肪族异氰酸酯为H 12MDI或IPDI中的一种或两种，且脂肪族异氰酸酯占异氰酸酯总量的0～20％。
  7. 根据权利要求6所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：以质量分数计，脂肪族异氰酸酯H 12MDI占聚氨酯预聚物组分的0～4.3％、IPDI占聚氨酯预聚物组分的0～9.3％；芳香族异氰酸酯MDI-100占聚氨酯预聚物组分的33.6～38.7％。
  8. 根据权利要求1所述的高透高弹聚氨酯弹性体的制备方法，其特征在于：聚氨酯弹性体的硬度邵A 65～95；回弹75～85％；透光率≧89％，最高达96％；雾度≦1.1％，最低达0.6％。
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