WO2020248765A1 - Method for preparing cellulose-based rigid polyurethane foam - Google Patents

Method for preparing cellulose-based rigid polyurethane foam Download PDF

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WO2020248765A1
WO2020248765A1 PCT/CN2020/090671 CN2020090671W WO2020248765A1 WO 2020248765 A1 WO2020248765 A1 WO 2020248765A1 CN 2020090671 W CN2020090671 W CN 2020090671W WO 2020248765 A1 WO2020248765 A1 WO 2020248765A1
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cellulose
polyether polyol
rigid foam
polyether
polyurethane rigid
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PCT/CN2020/090671
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French (fr)
Chinese (zh)
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周乐群
王金祥
黄东平
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红宝丽集团股份有限公司
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Publication of WO2020248765A1 publication Critical patent/WO2020248765A1/en

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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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers 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
    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons

Definitions

  • the invention belongs to the technical field of new materials, and specifically relates to a method for preparing cellulose-based polyurethane rigid foam.
  • Polyurethane rigid foam consists of rigid foam polyether polyol (hard foam combined polyether, also known as white material), and polymethylene polyphenyl polyisocyanate (PAPI) or diphenylmethane diisocyanate (MDI) (also known as Black material) prepared by reaction.
  • PAPI polymethylene polyphenyl polyisocyanate
  • MDI diphenylmethane diisocyanate
  • fluorine system rigid foam polyether polyol cyclopentane system rigid foam polyether polyol
  • water system rigid foam polyether polyol According to the field of use, it is divided into wood-like polyether, household appliance polyether, pipe polyether, sheet polyether, etc.
  • wood-like polyether is mainly used for wood-like products
  • home appliance polyether is mainly used for insulation of household appliances such as refrigerators and freezers
  • pipe polyether is mainly used for heat preservation of petroleum and heating pipes
  • sheet polyether is mainly used for preparing outer walls of cold storage. Insulation board products.
  • Polyether polyol is one of the main raw materials of polyurethane foam. It is prepared by addition polymerization reaction of initiator (compound with active hydrogen group) and epoxy compound (ethylene oxide, propylene oxide) .
  • initiator compound with active hydrogen group
  • epoxy compound ethylene oxide, propylene oxide
  • the functionality of polyether polyols obtained by adding initiators with different numbers of active hydrogen groups is very different. In the practical application of polyurethane products, several polyether polyols with different functionalities are usually added and mixed for use.
  • Zhang Meng et al. used hydroxymethyl rosin and glycerol (the mass of hydroxymethyl rosin accounted for 40-100%) as starting compounds, and KOH as a catalyst to conduct block polycondensation with propylene oxide and ethylene oxide.
  • the reaction product was purified to obtain a new type of rosin polyether polyol with different methylol rosin content and different epoxy chain links in color from brown to yellow. The performance was tested, and the viscosity and hydroxyl value of rigid polyurethane foam can be met.
  • Cellulose is an abundant natural resource on the earth.
  • the use of bio-based polyether to replace or partially replace non-renewable petroleum-based polyether foam is of great significance in leading the polyurethane industry to green, environmentally friendly and sustainable development.
  • the objective of the present invention is to provide a method for preparing cellulose-based polyurethane rigid foam, which uses lignocellulose to prepare cellulose-based polyether polyol and then to prepare polyurethane rigid foam. Realize the comprehensive utilization of lignocellulose and reduce the dependence of polyurethane on petroleum consumables.
  • a method for preparing cellulose-based polyurethane rigid foam The mixture containing polyether polyol, catalyst, foam stabilizer and blowing agent is used as white material, and polymethylene polyphenyl polyisocyanate (PAPI) or diphenyl Methane diisocyanate (MDI) is a black material. Mix the black material and white material, and stir and react until the foam is matured; wherein, the polyether polyol contains cellulose-based polyether polyol, and the cellulose-based polyether Polyols are prepared by using lignocellulose and glycerin as composite initiators, under the action of solvents and alkali metal catalysts, by block or random copolymerization with propylene oxide.
  • PAPI polymethylene polyphenyl polyisocyanate
  • MDI diphenyl Methane diisocyanate
  • Cellulose is a macromolecular polysaccharide composed of glucose. Each glucose residue ring contains 3 hydroxyl groups. It is a polyhydroxy compound and can be used as a starter for rigid foam polyether polyols. At the same time, cellulose is a natural macromolecular carbohydrate with a wide range of sources and is non-toxic. Polyether polyol synthesized from this as a raw material provides a sustainable raw material for the production of polyurethane rigid foam.
  • the main raw materials for polyurethane foaming include isocyanates, polyol compounds, and additives.
  • Polyols mainly include polyester and polyether.
  • the "one-step” process is more commonly used in the foaming process, where various materials are added at once and stirred evenly to make them foam.
  • the reaction equation is as follows:
  • Reaction (1) is an addition reaction.
  • the active hydrogen on the polyol first attacks the nitrogen atom on the isocyanate, and other atoms connected to the active hydrogen are added to the carbonyl group of the isocyanate.
  • the CO2 gas of reaction (2) can be used as a source of bubbles for foaming.
  • the catalyst is an amine catalyst, which can be dimethylcyclohexylamine (PC8), bis(2-dimethylaminoethyl) ether, triethylenediamine, N ,N,N',N'-tetramethylalkylene diamine, N,N,N',N"-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzyl Amine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, triethanolamine, N,N-dimethylethanolamine, etc., in an amount of 0.5 to 3.8 parts of polyether.
  • PC8 dimethylcyclohexylamine
  • bis(2-dimethylaminoethyl) ether triethylenediamine
  • N ,N,N',N'-tetramethylalkylene diamine N,N,N',N"-pentamethyldiethylenetriamine
  • triethylamine N,
  • the foam stabilizer is rigid foam silicone oil AK8801, and the amount is 2 to 3 parts in 100 parts of polyether.
  • the blowing agent is cyclopentane and water.
  • the amount of cyclopentane is 5-25% of the total polyether mass, and the amount of water is 0.5-3% of the total polyether mass.
  • the black material is polymeric MDI, and the mass ratio of the black material to the white material is 1 to 3:1.
  • the polyether polyol is composed of polyether polyol 450 and cellulose-based polyether polyol, wherein the mass ratio of polyether polyol 450 and cellulose-based polyether polyol is 10:1 to 5:5.
  • the appearance of the cellulose-based polyether polyol is a reddish-brown viscous liquid with a hydroxyl value of 203.13-332.91 mgKOH/g.
  • the cellulose-based polyurethane rigid foam prepared by the present invention adopts cellulose-based polyether polyol raw materials, which can reduce the cost of polyurethane rigid foam, improve the quality of polyurethane rigid foam, and realize lignocellulose
  • the high-efficiency utilization of the polyurethane foam has a good application prospect in the field of polyurethane rigid foam, conforms to the concept of green chemistry, and has good practicability.
  • the raw material polyether polyol 450 used in the present invention is industrial grade, produced by Nanjing Hongbaoli Co., Ltd.; silicone oil AK8801, is industrial grade, produced by Nanjing Meister Chemical Co., Ltd.; PC8 and PC41 are industrial grade, American Gas Chemical Product (China) Co., Ltd. production; cyclopentane is industrial grade; Shandong Liancheng Chemical Industry Co., Ltd. production; black polymer MDI (brand PM200) is industrial grade, Yantai Wanhua Chemical Co., Ltd.; cellulose-based polyether polyether Alcohol, homemade.
  • the appearance of the cellulose-based polyether polyol is a reddish-brown viscous liquid with a hydroxyl value of 271.26 mgKOH/g. Foam according to table 1 white material formula.
  • the polyurethane rigid foam process is as follows: use a mixture of polyether polyol, catalyst, foam stabilizer, foaming agent, etc. as the white material, and use PAPI or MDI (brand PM200) as the black material.
  • MDI is used as the black material
  • the white material The temperature of the black material and the black material are both 20°C, and the foaming process is at room temperature 20°C.
  • the appearance of the cellulose-based polyether polyol is a reddish-brown viscous liquid with a hydroxyl value of 332.91 mgKOH/g. Foam according to the white material formula in Table 1 and the process of Example 1.
  • the appearance of the cellulose-based polyether polyol is a reddish brown viscous liquid with a hydroxyl value of 203.13 mgKOH/g. According to table 1 white material formula and embodiment 1 process foaming.

Abstract

A method for preparing a cellulose-based rigid polyurethane foam. The cellulose-based rigid polyurethane foam comprises a raw material of cellulose-based polyether glycol. The costs of the rigid polyurethane foam can be lowered, the quality of the rigid polyurethane foam can be improved, and efficient utilization of lignocelluloses is achieved; the cellulose-based rigid polyurethane foam has good application prospects in the field of rigid polyurethane foams.

Description

一种纤维素基聚氨酯硬泡制备方法Method for preparing cellulose-based polyurethane rigid foam 技术领域Technical field
本发明属新材料技术领域，具体涉及一种纤维素基聚氨酯硬泡制备方法。The invention belongs to the technical field of new materials, and specifically relates to a method for preparing cellulose-based polyurethane rigid foam.
背景技术Background technique
聚氨酯硬质泡沫由硬泡聚醚多元醇(硬泡组合聚醚，又称白料)，与多亚甲基多苯基多异氰酸酯(PAPI)或二苯基甲烷二异氰酸酯(MDI)(又称黑料)反应制得。按组合聚醚种类分为氟体系硬泡聚醚多元醇、环戊烷体系硬泡聚醚多元醇、全水体系硬泡聚醚多元醇。按照使用领域分为仿木聚醚、家电聚醚、管道聚醚、板材聚醚等。其中仿木聚醚主要用于仿木材产品，家电聚醚主要用于冰箱、冷柜等家用电器保温，管道聚醚主要用于石油、供热管道的保温，板材聚醚主要用于制备冷库外墙保温板产品。Polyurethane rigid foam consists of rigid foam polyether polyol (hard foam combined polyether, also known as white material), and polymethylene polyphenyl polyisocyanate (PAPI) or diphenylmethane diisocyanate (MDI) (also known as Black material) prepared by reaction. According to the type of combined polyether, it can be divided into fluorine system rigid foam polyether polyol, cyclopentane system rigid foam polyether polyol, and water system rigid foam polyether polyol. According to the field of use, it is divided into wood-like polyether, household appliance polyether, pipe polyether, sheet polyether, etc. Among them, wood-like polyether is mainly used for wood-like products, home appliance polyether is mainly used for insulation of household appliances such as refrigerators and freezers, pipe polyether is mainly used for heat preservation of petroleum and heating pipes, and sheet polyether is mainly used for preparing outer walls of cold storage. Insulation board products.
聚醚多元醇(PPG)是聚氨酯泡沫的主要原料之一，由起始剂(具有活泼氢基团的化合物)与环氧化合物(环氧乙烷、环氧丙烷)经过加成聚合反应制得。通过加入活泼氢基团数目不同的起始剂得到聚醚多元醇的官能度有很大不同，在聚氨酯制品的实际应用中，通常会加入几种不同官能度的聚醚多元醇混合使用。Polyether polyol (PPG) is one of the main raw materials of polyurethane foam. It is prepared by addition polymerization reaction of initiator (compound with active hydrogen group) and epoxy compound (ethylene oxide, propylene oxide) . The functionality of polyether polyols obtained by adding initiators with different numbers of active hydrogen groups is very different. In the practical application of polyurethane products, several polyether polyols with different functionalities are usually added and mixed for use.
张猛等以羟甲基松香和丙三醇(羟甲基松香质量占40～100％)为起始化合物，以KOH为催化剂，与环氧丙烷和环氧乙烷进行嵌段缩聚反应，对反应产物进行提纯得到颜色由棕色到黄色的不同羟甲基松香含量和不同环氧链节的新型松香聚醚多元醇，对性能进行了测试，能够满足制备硬质聚氨酯泡沫塑料的粘度和羟值要求，并以多元醇、异氰酸酯，发泡剂(水、HCFC-141b)、表面活性剂、催化剂及其它助剂等为原料，采用一步法制备具有良好性能的新型松香硬质聚氨酯泡沫塑料。Zhang Meng et al. used hydroxymethyl rosin and glycerol (the mass of hydroxymethyl rosin accounted for 40-100%) as starting compounds, and KOH as a catalyst to conduct block polycondensation with propylene oxide and ethylene oxide. The reaction product was purified to obtain a new type of rosin polyether polyol with different methylol rosin content and different epoxy chain links in color from brown to yellow. The performance was tested, and the viscosity and hydroxyl value of rigid polyurethane foam can be met. Requirements, and use polyols, isocyanates, blowing agents (water, HCFC-141b), surfactants, catalysts and other additives as raw materials, and adopt a one-step process to prepare new rosin rigid polyurethane foams with good performance.
纤维素是地球上丰富的自然资源，以生物基聚醚代替或部分代替不可再生的石油基聚醚发泡，在引领聚氨酯工业向绿色、环保、可持续发展方向上，具有重大意义。尚未见使用以纤维素为原料制备聚醚多元醇并用于聚氨酯制备的报道。Cellulose is an abundant natural resource on the earth. The use of bio-based polyether to replace or partially replace non-renewable petroleum-based polyether foam is of great significance in leading the polyurethane industry to green, environmentally friendly and sustainable development. There is no report about the use of cellulose as a raw material to prepare polyether polyols and use them in polyurethane preparation.
发明内容Summary of the invention
发明目的：针对现有技术中存在的不足，本发明的目的是提供一种纤维素基聚氨酯硬泡的制备方法，以木质纤维素制备纤维素基聚醚多元醇进而制备聚氨酯硬质泡沫，以期实现木质纤维素的综合利用，降低聚氨酯对石油消耗品的依赖。Objective of the invention: In view of the shortcomings in the prior art, the objective of the present invention is to provide a method for preparing cellulose-based polyurethane rigid foam, which uses lignocellulose to prepare cellulose-based polyether polyol and then to prepare polyurethane rigid foam. Realize the comprehensive utilization of lignocellulose and reduce the dependence of polyurethane on petroleum consumables.
技术方案：为了实现上述发明目的，本发明采用的技术方案为：Technical solution: In order to achieve the above-mentioned purpose of the invention, the technical solution adopted by the present invention is:
一种纤维素基聚氨酯硬泡制备方法，以包含有聚醚多元醇、催化剂、泡沫稳定剂、发泡剂的混合物为白料，以多亚甲基多苯基多异氰酸酯(PAPI)或二苯基甲烷二异氰酸酯(MDI)为黑料，将黑料与白料混合，搅拌反应直至泡沫熟化；其中，在聚醚多元醇中含有纤维素基聚醚多元醇，所述的纤维素基聚醚多元醇，以木质纤维素和甘油为复合起始剂，在溶剂、碱金属催化剂作用下，与环氧丙烷进行嵌段或无规共聚而制得。A method for preparing cellulose-based polyurethane rigid foam. The mixture containing polyether polyol, catalyst, foam stabilizer and blowing agent is used as white material, and polymethylene polyphenyl polyisocyanate (PAPI) or diphenyl Methane diisocyanate (MDI) is a black material. Mix the black material and white material, and stir and react until the foam is matured; wherein, the polyether polyol contains cellulose-based polyether polyol, and the cellulose-based polyether Polyols are prepared by using lignocellulose and glycerin as composite initiators, under the action of solvents and alkali metal catalysts, by block or random copolymerization with propylene oxide.
纤维素是由葡萄糖组成的大分子多糖，其中每个葡萄糖残基环均含有3个羟基，是一种多羟基化合物，可用作硬泡聚醚多元醇的起始剂。同时纤维素是天然高分子碳水化合物，来源广泛，本身无毒性，以此为原料合成的聚醚多元醇，为聚氨酯硬质泡沫生产提供了一种可持续性的原料。Cellulose is a macromolecular polysaccharide composed of glucose. Each glucose residue ring contains 3 hydroxyl groups. It is a polyhydroxy compound and can be used as a starter for rigid foam polyether polyols. At the same time, cellulose is a natural macromolecular carbohydrate with a wide range of sources and is non-toxic. Polyether polyol synthesized from this as a raw material provides a sustainable raw material for the production of polyurethane rigid foam.
聚氨酯发泡的主要原料包括异氰酸酯、多元醇化合物、助剂。多元醇主要包括聚酯和聚醚两大类。目前，发泡工艺较为普遍的采用“一步法”工艺，将各种物料一次性加入后，搅拌均匀，使之发泡。反应方程式如下：The main raw materials for polyurethane foaming include isocyanates, polyol compounds, and additives. Polyols mainly include polyester and polyether. At present, the "one-step" process is more commonly used in the foaming process, where various materials are added at once and stirred evenly to make them foam. The reaction equation is as follows:
R-NCO+R/-OH→RNHCOOR /     (1) R-NCO+R/-OH→RNHCOOR / (1)
2R-NCO+H 2O→RNHCONHR+CO 2↑  (2) 2R-NCO+H 2 O→RNHCONHR+CO 2 ↑ (2)
反应(1)是一个加成反应，多元醇上的活泼氢首先进攻异氰酸酯上的氮原子，和活泼氢相连的其他原子则加成到异氰酸酯的羰基上。Reaction (1) is an addition reaction. The active hydrogen on the polyol first attacks the nitrogen atom on the isocyanate, and other atoms connected to the active hydrogen are added to the carbonyl group of the isocyanate.
反应(2)的CO2气体可以作为发泡用的气泡来源。The CO2 gas of reaction (2) can be used as a source of bubbles for foaming.
优选的，本发明聚氨酯硬质泡沫制备配方中，催化剂为胺类催化剂，可以是二甲基环己胺(PC8)、双(2-二甲氨基乙基)醚、三亚乙基二胺、N,N,N',N'-四甲基亚烷基二胺、N,N,N',N”-五甲基二亚乙基三胺、三乙胺、N,N-二甲基苄胺、N,N-二甲基十六胺、N,N-二甲基丁胺、三乙醇胺、N,N-二甲基乙醇胺等，用量为100份聚醚中加入0.5～3.8份。Preferably, in the polyurethane rigid foam preparation formula of the present invention, the catalyst is an amine catalyst, which can be dimethylcyclohexylamine (PC8), bis(2-dimethylaminoethyl) ether, triethylenediamine, N ,N,N',N'-tetramethylalkylene diamine, N,N,N',N"-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzyl Amine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, triethanolamine, N,N-dimethylethanolamine, etc., in an amount of 0.5 to 3.8 parts of polyether.
优选的，本发明聚氨酯硬质泡沫制备配方中，泡沫稳定剂为硬泡硅油AK8801，用量为100份聚醚中加入2～3份。Preferably, in the polyurethane rigid foam preparation formula of the present invention, the foam stabilizer is rigid foam silicone oil AK8801, and the amount is 2 to 3 parts in 100 parts of polyether.
优选的，本发明聚氨酯硬质泡沫制备配方中，发泡剂为环戊烷和水。环戊烷用量为总聚醚质量的5～25％，水用量为总聚醚质量的0.5～3％。Preferably, in the formulation for preparing the rigid polyurethane foam of the present invention, the blowing agent is cyclopentane and water. The amount of cyclopentane is 5-25% of the total polyether mass, and the amount of water is 0.5-3% of the total polyether mass.
优选的，本发明聚氨酯硬质泡沫制备配方中，黑料为聚合MDI，黑料与白料的质量配比为1～3:1。Preferably, in the preparation formula of the polyurethane rigid foam of the present invention, the black material is polymeric MDI, and the mass ratio of the black material to the white material is 1 to 3:1.
优选的，聚醚多元醇由聚醚多元醇450和纤维素基聚醚多元醇组成，其中聚醚多元醇450和纤维素基聚醚多元醇的质量比为10:1～5:5。Preferably, the polyether polyol is composed of polyether polyol 450 and cellulose-based polyether polyol, wherein the mass ratio of polyether polyol 450 and cellulose-based polyether polyol is 10:1 to 5:5.
优选的，纤维素基聚醚多元醇外观为红褐色粘稠液体，羟值为203.13-332.91mgKOH/g。Preferably, the appearance of the cellulose-based polyether polyol is a reddish-brown viscous liquid with a hydroxyl value of 203.13-332.91 mgKOH/g.
有益效果：与现有技术相比，本发明制备的纤维素基聚氨酯硬泡，采用纤维素基聚醚多元醇原料，可降低聚氨酯硬泡成本，提高聚氨酯硬泡品质，并实现了木质纤维素的高效利用，在聚氨酯硬泡领域中有良好的应用前景，符合绿色化学的理念，具有很好的实用性。Beneficial effects: Compared with the prior art, the cellulose-based polyurethane rigid foam prepared by the present invention adopts cellulose-based polyether polyol raw materials, which can reduce the cost of polyurethane rigid foam, improve the quality of polyurethane rigid foam, and realize lignocellulose The high-efficiency utilization of the polyurethane foam has a good application prospect in the field of polyurethane rigid foam, conforms to the concept of green chemistry, and has good practicability.
具体实施方式Detailed ways
下面通过实施例进一步描述本发明，但未限于所举的实施例。The following examples further describe the present invention, but are not limited to the examples cited.
本发明使用的原料聚醚多元醇450为工业级，南京红宝丽股份有限公司生产；硅油AK8801，为工业级，南京美思德化学股份有限公司生产；PC8、PC41为工业级，美国气体化工产品(中国)有限公司生产；环戊烷为工业级；山东联成化学工业有限公司生产；黑料聚合MDI(牌号PM200)为工业级，烟台万华化学股份有限公司；纤维素基聚醚多元醇，自制。The raw material polyether polyol 450 used in the present invention is industrial grade, produced by Nanjing Hongbaoli Co., Ltd.; silicone oil AK8801, is industrial grade, produced by Nanjing Meister Chemical Co., Ltd.; PC8 and PC41 are industrial grade, American Gas Chemical Product (China) Co., Ltd. production; cyclopentane is industrial grade; Shandong Liancheng Chemical Industry Co., Ltd. production; black polymer MDI (brand PM200) is industrial grade, Yantai Wanhua Chemical Co., Ltd.; cellulose-based polyether polyether Alcohol, homemade.
检测：在室温20℃条件下，将36g黑料(聚合MDI)与30g白料(聚醚)以1.2:1混合倒入200mL塑料杯中，搅拌5s，记录下乳白上升时间、拉丝时间，泡沫熟化1h后，测泡沫密度，观察泡孔。Detection: Under the condition of room temperature and 20℃, mix 36g black material (polymeric MDI) and 30g white material (polyether) into a 200mL plastic cup at a 1.2:1 ratio, stir for 5s, record the milky white rise time, wire drawing time, and foam After curing for 1 hour, measure the foam density and observe the cells.
根据国标GB/T12008.3-2009聚醚多醇中羟值测定方法检测纤维素基聚醚多元醇的羟值，根据国标GB/T6343-95检测泡沫的密度。Detect the hydroxyl value of cellulose-based polyether polyol according to the national standard GB/T12008.3-2009 method for determining the hydroxyl value of polyether polyols, and detect the density of foam according to the national standard GB/T6343-95.
实施例1Example 1
纤维素基聚醚多元醇外观为红褐色粘稠液体，羟值为271.26mgKOH/g。按表1白料配方发泡。The appearance of the cellulose-based polyether polyol is a reddish-brown viscous liquid with a hydroxyl value of 271.26 mgKOH/g. Foam according to table 1 white material formula.
表1纤维素基聚醚多元醇替代部分聚醚多元醇450发泡配方Table 1 Cellulose-based polyether polyol replaces part of polyether polyol 450 foaming formula
组份配方Component formula 11 22 33 44 55
聚醚多元醇450Polyether Polyol 450 100份100 servings 90份90 servings 80份80 servings 70份70 servings 60份60 servings
纤维素基聚醚多元醇Cellulose-based polyether polyol 0份0 copies 10份10 servings 20份20 servings 30份30 servings 40份40 servings
AK8801AK8801 2份2 servings 2份2 servings 2份2 servings 2份2 servings 2份2 servings
PC8PC8 2份2 servings 2份2 servings 2份2 servings 2份2 servings 2份2 servings
PC41PC41 0.5份0.5 serving 0.5份0.5 serving 0.5份0.5 serving 0.5份0.5 serving 0.5份0.5 serving
环戊烷Cyclopentane 15份15 servings 15份15 servings 15份15 servings 15份15 servings 15份15 servings
水water 1.5份1.5 servings 1.5份1.5 servings 1.5份1.5 servings 1.5份1.5 servings 1.5份1.5 servings
聚氨酯硬泡工艺为：以聚醚多元醇、催化剂、泡沫稳定剂、发泡剂等混合物为白料，以PAPI或MDI(牌号PM200)为黑料，本实施例中选用MDI为黑料，白料和黑料的温度均为20℃，发泡工艺为室温20℃，将黑料(MDI)与白料(聚醚)以质量比1.2:1混合倒入200mL塑料杯中，搅拌5s，记录下乳白上升时间、拉丝时间，泡沫熟化0.5h后，测泡沫密度，观察泡孔。The polyurethane rigid foam process is as follows: use a mixture of polyether polyol, catalyst, foam stabilizer, foaming agent, etc. as the white material, and use PAPI or MDI (brand PM200) as the black material. In this embodiment, MDI is used as the black material, and the white material The temperature of the black material and the black material are both 20℃, and the foaming process is at room temperature 20℃. Mix the black material (MDI) and white material (polyether) with a mass ratio of 1.2:1 into a 200mL plastic cup, stir for 5 seconds, and record Measure the density of the foam and observe the cells after the foam is matured for 0.5h after the rise time of the lower milky white and the drawing time.
表2发泡结果Table 2 Foaming results
Figure PCTCN2020090671-appb-000001
Figure PCTCN2020090671-appb-000001
结果如表2所示，随着纤维素基聚醚多元醇用量的增加，当用量达到30％时，开始出现泡孔变粗的现象，该纤维素基聚醚多元醇具有较好的开孔作用。纤维素基聚醚多元醇用量从0提高到40％时，乳白时间从12s缩短到9s；拉丝时间从91s缩短到74s；泡沫密度从25.7kg/m 3降低到25.2kg/m 3，然后随着泡孔变粗，密度又提升到27.4kg/m 3，各项指标变化较为明显。 The results are shown in Table 2. As the amount of cellulose-based polyether polyol increases, when the amount reaches 30%, the cells begin to become coarse. The cellulose-based polyether polyol has better openings. effect. When the dosage of cellulose-based polyether polyol is increased from 0 to 40%, the whitening time is shortened from 12s to 9s; the drawing time is shortened from 91s to 74s; the foam density is reduced from 25.7kg/m 3 to 25.2kg/m 3 , and then The pores become thicker and the density increases to 27.4kg/m 3 , and the changes in various indicators are more obvious.
实施例2Example 2
纤维素基聚醚多元醇外观为红褐色粘稠液体，羟值332.91mgKOH/g。按表1白料配方和实施例1的工艺发泡。The appearance of the cellulose-based polyether polyol is a reddish-brown viscous liquid with a hydroxyl value of 332.91 mgKOH/g. Foam according to the white material formula in Table 1 and the process of Example 1.
表3纤维素基聚醚多元醇部分替代聚醚多元醇450发泡结果Table 3 Cellulose-based polyether polyol partially replaced polyether polyol 450 foaming results
Figure PCTCN2020090671-appb-000002
Figure PCTCN2020090671-appb-000002
结果如表3所示，随着纤维素基聚醚多元醇用量增加，当用量达到30％时，出现泡孔由细腻变为一般。纤维素基聚醚多元醇用量从0提高到40％时，乳白时间从12s缩短到10s，变化不明显；拉丝时间从91s缩短到85s；泡沫密度基本维持在25.0kg/m 3左右。 The results are shown in Table 3. As the amount of cellulose-based polyether polyol increases, when the amount reaches 30%, the cells change from fine to normal. When the amount of cellulose-based polyether polyol is increased from 0 to 40%, the whitening time is shortened from 12s to 10s, and the change is not obvious; the drawing time is shortened from 91s to 85s; the foam density is basically maintained at about 25.0kg/m 3 .
实施例3Example 3
纤维素基聚醚多元醇外观为红褐色粘稠液体，羟值203.13mgKOH/g。按表1白料配方和实施例1工艺发泡。The appearance of the cellulose-based polyether polyol is a reddish brown viscous liquid with a hydroxyl value of 203.13 mgKOH/g. According to table 1 white material formula and embodiment 1 process foaming.
表4纤维素基聚醚多元醇替代部分450发泡结果Table 4 Cellulose-based polyether polyol replaced part of 450 foaming results
Figure PCTCN2020090671-appb-000003
Figure PCTCN2020090671-appb-000003
结果如表4所示，随着纤维素基聚醚多元醇用量增加，当用量达到20％时，开始出现泡沫颜色发黄，当用量达到30％时泡孔变粗和内部开裂的现象，用量的增加对泡孔有一定的副作用。纤维素基聚醚多元醇用量从0提高到40％时，乳白时间从12s缩短到8s，变化较大；拉丝时间从91s缩短到73s，变化较大；泡沫密度从25.7kg/m 3升高到31.9kg/m 3。 The results are shown in Table 4. As the amount of cellulose-based polyether polyol increases, when the amount reaches 20%, the foam color starts to turn yellow, and when the amount reaches 30%, the cells become thick and internal cracks. The increase in pores has certain side effects. When the amount of cellulose-based polyether polyol is increased from 0 to 40%, the whitening time is shortened from 12s to 8s, which is a big change; the drawing time is shortened from 91s to 73s, which is a big change; the foam density is increased from 25.7kg/m 3 To 31.9kg/m 3 .
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited to this. Anyone familiar with the technical field within the technical scope disclosed by the present invention, according to the technical solution of the present invention The equivalent replacement or change of the inventive concept thereof shall be covered by the protection scope of the present invention.

Claims (7)

  1. 一种纤维素基聚氨酯硬泡制备方法，其特征在于，以含有聚醚多元醇、催化剂、泡沫稳定剂、发泡剂的混合物为白料，以多亚甲基多苯基多异氰酸酯或二苯基甲烷二异氰酸酯为黑料，将黑料与白料混合，搅拌反应直至泡沫熟化；其中，在聚醚多元醇中含有纤维素基聚醚多元醇，所述的纤维素基聚醚多元醇，以木质纤维素和甘油为复合起始剂，在溶剂、碱金属催化剂作用下，与环氧丙烷进行嵌段或无规共聚而制得。A method for preparing cellulose-based polyurethane rigid foam, which is characterized in that a mixture containing polyether polyol, catalyst, foam stabilizer, and foaming agent is used as white material, and polymethylene polyphenyl polyisocyanate or diphenyl Methane diisocyanate is a black material. Mix the black material and the white material, and stir and react until the foam matures; wherein, the polyether polyol contains cellulose-based polyether polyol, and the cellulose-based polyether polyol is It is prepared by using lignocellulose and glycerin as a composite initiator, under the action of a solvent and an alkali metal catalyst, and propylene oxide for block or random copolymerization.
  2. 根据权利要求1所述的纤维素基聚氨酯硬泡制备方法，其特征在于，所述的催化剂为胺类催化剂，用量为总聚醚质量的0.5～3.8％，所述催化剂为二甲基环己胺、双(2-二甲氨基乙基)醚、三亚乙基二胺、N,N,N',N'-四甲基亚烷基二胺、N,N,N',N”-五甲基二亚乙基三胺、三乙胺、N,N-二甲基苄胺、N,N-二甲基十六胺、N,N-二甲基丁胺、三乙醇胺、N,N-二甲基乙醇胺或N,N-二甲基环己胺中的一种或多种。The method for preparing cellulose-based polyurethane rigid foam according to claim 1, wherein the catalyst is an amine catalyst, and the amount is 0.5 to 3.8% of the total polyether mass, and the catalyst is dimethylcyclohexane. Amine, bis(2-dimethylaminoethyl) ether, triethylenediamine, N,N,N',N'-tetramethylalkylenediamine, N,N,N',N”-penta Methyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, triethanolamine, N,N -One or more of dimethylethanolamine or N,N-dimethylcyclohexylamine.
  3. 根据权利要求1所述的纤维素基聚氨酯硬泡制备方法，其特征在于，所述的泡沫稳定剂为南京美思德的硬泡硅油AK8801，用量为总聚醚质量的2～3％。The method for preparing cellulose-based polyurethane rigid foam according to claim 1, wherein the foam stabilizer is the rigid foam silicone oil AK8801 of Nanjing Meiside, and the amount is 2 to 3% of the total polyether mass.
  4. 根据权利要求1所述的纤维素基聚氨酯硬泡制备方法，其特征在于，所述的发泡剂为环戊烷和水的混合物；其中，环戊烷用量为总聚醚质量的5～25％，水用量为总聚醚质量的0.5～3％。The method for preparing cellulose-based polyurethane rigid foam according to claim 1, wherein the blowing agent is a mixture of cyclopentane and water; wherein the amount of cyclopentane is 5-25 of the total polyether mass. %, the amount of water is 0.5-3% of the total polyether mass.
  5. 根据权利要求1所述的纤维素基聚氨酯硬泡制备方法，其特征在于，聚醚多元醇由聚醚多元醇450和纤维素基聚醚多元醇组成，其中聚醚多元醇450和纤维素基聚醚多元醇的质量比为10:1～5:5。The method for preparing cellulose-based polyurethane rigid foam according to claim 1, wherein the polyether polyol is composed of polyether polyol 450 and cellulose-based polyether polyol, wherein polyether polyol 450 and cellulose-based The mass ratio of polyether polyol is 10:1 to 5:5.
  6. 根据权利要求1所述的纤维素基聚氨酯硬泡制备方法，其特征在于，黑料为聚合MDI，黑料与白料的质量配比为(1～3):1。The method for preparing cellulose-based polyurethane rigid foam according to claim 1, wherein the black material is polymerized MDI, and the mass ratio of the black material to the white material is (1 to 3):1.
  7. 根据权利要求1所述的纤维素基聚氨酯硬泡制备方法，其特征在于，纤维素基聚醚多元醇外观为红褐色粘稠液体，羟值为203.13-332.91mgKOH/g。The method for preparing cellulose-based polyurethane rigid foam according to claim 1, wherein the cellulose-based polyether polyol has an appearance of a reddish-brown viscous liquid with a hydroxyl value of 203.13-332.91 mgKOH/g.
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