CN104497264B - Preparation method rich in PAPI polyurethane high resilience foam materials - Google Patents

Preparation method rich in PAPI polyurethane high resilience foam materials Download PDF

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CN104497264B
CN104497264B CN201410750998.7A CN201410750998A CN104497264B CN 104497264 B CN104497264 B CN 104497264B CN 201410750998 A CN201410750998 A CN 201410750998A CN 104497264 B CN104497264 B CN 104497264B
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component
foam
papi
agent
preparation
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CN104497264A (en
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夏瑞军
陆备峰
韩志峰
朱军伟
汤国均
於汉辉
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ZHOUSHAN YINDAI AUTO PARTS Co Ltd
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ZHOUSHAN YINDAI AUTO PARTS Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
    • C08G18/16—Catalysts
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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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
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    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
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    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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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

A kind of preparation method rich in PAPI polyurethane high resilience foam materials, comprises the following steps：Component A and B component are stirred at least 1 hour in the reactor of high-pressure foam agent respectively, foam mold is warmed to 50~70 DEG C, and on foam mold inwall even application releasing agent, then component A and B component by weight 100: 50~70 is dosed into mould by foaming machine high pressure mixing, matched moulds is cured 3~8 minutes, and then the demoulding, deburring are finished product successively；The advantage of the invention is that, using the raw material containing multiple reactive hydrogens as initiator, using expoxy propane (PO) and oxirane (EO), obtained polyalcohol is used as modifying agent under high temperature polymerization reaction, adjust the foamable reaction sequence of the foam based on MDI bases (PAPI), foamable reaction is set to compare balance, soft and hard segments distribution is relatively reasonable, enable the obtained foam based on MDI bases (PAPI) that there is good high resilience, expansion ratio is high, elongation percentage and tearing strength are high, it is often more important that the foamed material sense of touch prepared using formula is good.

Description

Preparation method rich in PAPI polyurethane high resilience foam materials
Technical field
Of the invention and a kind of foamed material manufacture technology field, it is especially a kind of to be rich in PAPI polyurethane high resilience foam materials The preparation method of material.
Background technology
Traditional polyurethane high resilience foam is more based on TDI bases, and its product has a good mechanical performance, but cost compared with Height, has a certain impact to environment and career safety ＆ health.Although polyurethane high resilience foam based on MDI bases (PAPI) has Cost advantage, and have certain contribution to environment and career safety ＆ health, but expansion ratio is low, resilience, elongation percentage, and tear is strong Degree difference and it is difficult to low-density, the improvement so its preparation method needs.
The content of the invention
The technical problems to be solved by the invention are that a kind of expansion ratio height is provided for above-mentioned state of the art, are returned Elastic good, elongation percentage and the high preparation method rich in PAPI polyurethane high resilience foam materials of tearing strength.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：This is rich in PAPI polyurethane high resilience foam materials The preparation method of material, it is characterised in that：Comprise the following steps：By component A and B component respectively in the reactor of high-pressure foam agent Stirring at least 1 hour, is warmed to 50~70 DEG C, and the releasing agent on foam mold inwall even application, then by foam mold Component A and B component by weight 100: 50~70 is dosed into mould by foaming machine high pressure mixing, matched moulds cures 3~8 points Clock, then the demoulding, deburring are finished product successively；The proportioning of the component A is：Polyethers 330N：33~60%, polymer polyol Alcohol：33~60%, silicone oil：0.5~1.5%, catalyst A33：0.2~0.8%, catalyst A-1：0.2~0.8%, it is used as friendship Join the diethanol amine of agent：0.5~3.0%, polyalcohol auxiliary agent DJ002：3~10%, it is used as the water of foaming agent：2.5~6%；Institute The proportioning for stating B component is：Toluene di-isocyanate(TDI)：0~40%, polymethylene multi-phenenyl isocyanate：60~100%, it is described Percentage is weight percentage.
Above-mentioned catalyst A33：The solution being formulated by triethylenediamine and dipropylene glycol.
As an improvement, the component ratio of the triethylenediamine and dipropyleneglycol solution is preferably：Triethylene Diamines is 33%, and dipropylene glycol is 67%, and the percentage is weight percentage.
Above-mentioned catalyst A-1：The solution being formulated by double dimethylaminoethyl ethers and dipropylene glycol.
As an improvement, the component ratio of described pair of dimethylaminoethyl ether and dipropyleneglycol solution is preferably：Double two Methylaminoethyl ether is 70%, and dipropylene glycol is 30%, and the percentage is weight percentage.
As an improvement, the preparation method of the polyalcohol auxiliary agent DJ002 is：Using the raw material containing active hydrogen atom as starting Agent, the raw material containing active hydrogen atom includes glycerine, sucrose, diethanol amine, triethanolamine, trimethylolpropane, Ji Wusi PO, then polymerize and the polyether polyols that hydroxyl value is 15~30mgKOH/g is made by one kind in alcohol and glucitol compounds with EO Alcohol, when wherein PO polymerize with EO, PO accounts for 15~100% percentage by weights, and EO accounts for 0~85% percentage by weight, and the PO is ring Ethylene Oxide, the EO is oxirane.
Prior art is compared, it is an advantage of the current invention that using the raw material containing multiple reactive hydrogens as initiator, with expoxy propane (PO), as modifying agent, adjusted with oxirane (EO) obtained polyalcohol under high temperature polymerization reaction based on MDI bases (PAPI) Foam foamable reaction sequence, foamable reaction is compared balance, soft and hard segments distribution is relatively reasonable, solve above-mentioned a series of ask Topic, enables the obtained foam based on MDI bases (PAPI) to have good high resilience, and expansion ratio is high, elongation percentage and tears Resistance to spalling is high, it is often more important that the foamed material sense of touch prepared using formula is good, and comfortableness is obviously improved.
Embodiment
The present invention is described in further detail with reference to embodiments.
The preparation method rich in PAPI polyurethane high resilience foam materials of the present embodiment, comprises the following steps：By component A Stirred respectively in the reactor of high-pressure foam agent at least 1 hour with B component, foam mold is warmed to 50~70 DEG C, and Releasing agent on foam mold inwall even application, then by component A and B component by weight 100: 50~70 by foaming machine high pressure Mixed material feeding is into mould, and matched moulds is cured 3~8 minutes, and then the demoulding, deburring are finished product successively；The proportioning of the component A For：Polyethers 330N：33~60%, polymer polyatomic alcohol：33~60%, silicone oil：0.5~1.5%, catalyst A33：0.2~ 0.8%, catalyst A-1：0.2~0.8%, it is used as the diethanol amine of crosslinking agent：0.5~3.0%, polyalcohol auxiliary agent DJ002：3 ~10%, it is used as the water of foaming agent：2.5~6%；The proportioning of the B component is：Toluene di-isocyanate(TDI)：0~40%, it is more sub- The many phenyl isocyanates of methyl：60~100%.The catalyst A33：Prepared by triethylenediamine and dipropylene glycol and Into solution.The component ratio of the triethylenediamine and dipropyleneglycol solution is：Triethylenediamine is 33%, a contracting DPG is 67%.The catalyst A-1：The solution being formulated by double dimethylaminoethyl ethers and dipropylene glycol. The component ratio of described pair of dimethylaminoethyl ether and dipropyleneglycol solution is：Double dimethylaminoethyl ethers are 70%, a contracting DPG is 30%, and the percentage is weight percentage.The preparation method of the polyalcohol auxiliary agent DJ002 is：With containing work Property hydrogen atom raw material be initiator, the raw material containing active hydrogen atom include glycerine, sucrose, diethanol amine, triethanolamine, One kind in trimethylolpropane, pentaerythrite and glucitol compounds, then PO is polymerize with EO and be made hydroxyl value be 15~ 30mgKOH/g PPG, when wherein PO polymerize with EO, PO accounts for 15~100% percentage by weights, and EO accounts for 0~85% weight Percentage is measured, the PO is expoxy propane, and the EO is oxirane.
By prepared by this method (table 1) is contrasted rich in PAPI foaming properties
Regular convention formula Plus DJ002 formulas
Foam density 45~65kg/m3 38~65kg/m3
Indentation force deflection (ILD 65%) ＞ 500N/323cm2 ＞ 500N/323cm2
65%/25% collapses rate ＞ 2.5 ＞ 2.8
75% compression set ＜ 20% ＜ 15%
Elongation percentage ＞ 50% ＞ 60%
Tearing strength ＞ 2.5N/cm ＞ 2.5N/cm
Rebound degree ＞ 40% ＞ 45%
Table 2 is used for the formula (content of component is in parts by weight) and foaming properties for preparing foam
Low-density from foam can be seen that by the performance of table 1 or the embodiment contrast product of table 2, comfortableness is returned From the point of view of bullet rate situation, technology of the invention has obvious advantage.
Above-mentioned improvement expands PAPI and TDI mixing proportion scope, so, and people can be according to TDI/PAPI valencys Lattice change, and choose the more preferable mixing proportion of cost performance, can be effectively reduced production cost.PAPI therein and the hydroxyl value are Hydroxyl value in 15~30mgKOH/g is the known technology of the art, is not described further in detail herein.

Claims (1)

1. a kind of preparation method rich in PAPI polyurethane high resilience foam materials, it is characterised in that：Comprise the following steps：By A Component is stirred at least 1 hour in the reactor of high-pressure foam agent respectively with B component, and foam mold is warmed into 50~70 DEG C, And on foam mold inwall even application releasing agent, then by component A and B component by weight 100：50~70 by foaming machine High pressure mixing is dosed into mould, and matched moulds is cured 3~8 minutes, and then the demoulding, deburring are finished product successively；The component A is matched somebody with somebody Than for：Polyethers 330N：33~60%, polymer polyatomic alcohol：33~60%, silicone oil：0.5~1.5%, catalyst A33：0.2~ 0.8%, catalyst A-1：0.2~0.8%, it is used as the diethanol amine of crosslinking agent：0.5~3.0%, polyalcohol auxiliary agent DJ002：3 ~10%, it is used as the water of foaming agent：2.5~6%；The proportioning of the B component is：Toluene di-isocyanate(TDI)：0~40%, it is more sub- The many phenyl isocyanates of methyl：60~100%, the catalyst A33：Prepared by triethylenediamine and dipropylene glycol and Into solution；The component ratio of the triethylenediamine and dipropyleneglycol solution is：Triethylenediamine is 33%, a contracting DPG is 67%, the catalyst A-1：The solution being formulated by double dimethylaminoethyl ethers and dipropylene glycol； The component ratio of described pair of dimethylaminoethyl ether and dipropyleneglycol solution is：Double dimethylaminoethyl ethers are 70%, a contracting DPG is 30%, and the percentage is weight percentage；The preparation method of the polyalcohol auxiliary agent DJ002 is：With containing work Property hydrogen atom raw material be initiator, the raw material containing active hydrogen atom include glycerine, sucrose, diethanol amine, triethanolamine, One kind in trimethylolpropane, pentaerythrite and glucitol compounds, then PO is polymerize with EO and be made hydroxyl value be 15~ 30mgKOH/g PPG, when wherein PO polymerize with EO, PO accounts for 15~100% percentage by weights, and EO accounts for 0~85% weight Percentage is measured, the PO is expoxy propane, and the EO is oxirane.
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CN107353388A (en) * 2017-06-27 2017-11-17 重庆市宏立摩托车制造有限公司 High flame retardant high-rebound polyurethane seat foam composition and foam process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1274375A (en) * 1997-08-11 2000-11-22 亨茨曼Ici化学品有限公司 Novel polyurethane foam compsn. having improved flex fatigue
CN1513892A (en) * 2003-06-13 2004-07-21 张汉林 High reelastic polyurethane shaped foam
CN101205288B (en) * 2006-12-22 2011-09-07 比亚迪股份有限公司 Polyurethane foam compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1274375A (en) * 1997-08-11 2000-11-22 亨茨曼Ici化学品有限公司 Novel polyurethane foam compsn. having improved flex fatigue
CN1513892A (en) * 2003-06-13 2004-07-21 张汉林 High reelastic polyurethane shaped foam
CN101205288B (en) * 2006-12-22 2011-09-07 比亚迪股份有限公司 Polyurethane foam compositions

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