阅读说明：本技术 聚氨酯软质泡沫 (Polyurethane flexible foam ) 是由 童俊 于 2018-06-27 设计创作，主要内容包括：本发明涉及一种制备软质高回弹聚氨酯泡沫的方法、由该方法制得的软质高回弹聚氨酯泡沫以及该泡沫在汽车座椅坐垫/靠垫方面的用途。该软质高回弹聚氨酯泡沫由包括异氰酸酯和多元醇,以及至少一种氨基封端的长链扩链剂、发泡剂和催化剂等组分的反应体系制得。本发明的聚氨酯反应体系熟化快、脱模时间短,所得泡沫弹性好、舒适度高,而且还具有满意的低气味。(The invention relates to a method for producing a flexible high-resilience polyurethane foam, to a flexible high-resilience polyurethane foam produced by said method, and to the use of said foam in vehicle seat cushions/cushions. The soft high-resilience polyurethane foam is prepared from a reaction system comprising isocyanate, polyol, at least one amino-terminated long-chain extender, a foaming agent, a catalyst and the like. The polyurethane reaction system of the invention has the advantages of fast curing, short demoulding time, good elasticity of the obtained foam, high comfort level and satisfactory low odor.)

1. A process for preparing a flexible high resilience polyurethane foam by reacting a reaction system comprising:

component A isocyanate;

component B, comprising:

a polyol;

a foaming agent;

at least one amine catalyst; and

at least one amino-terminated long-chain extender having a functionality of 2 to 3, an ammonia number of 10 to 500mg KOH/g, preferably 20 to 450mg KOH/g, particularly preferably 28 to 350mg KOH/g (determined according to ASTM D2074-.

2. Process according to claim 1, characterized in that the amino-terminated long chain extender is present in an amount of 1 to 20pbw, preferably 1 to 17pbw, particularly preferably 2 to 15pbw, based on the weight of component B.

3. A process according to claim 1 or claim 2 characterised in that the amino terminated long chain extender is a polyetheramine.

4. A process according to claim 1 or 2, characterized in that the reaction is carried out in a mould and the polyurethane foam has a minimum demold time of < 4 minutes, preferably < 3.5 minutes.

5. The process according to claim 1 or 2, characterized in that the polyol is selected from one or both of the following polyether polyols:

B1) a glycerol-initiated, EO-tipped long-chain polyether polyol having a functionality of 3 and a weight-average molecular weight of 4000 to 9000g/mol, preferably 4500 to 8500g/mol, particularly preferably 5000 to 8000g/mol (test method reference GB/T21863-2008), in an amount of 50 to 85pbw, preferably 60 to 85pbw, particularly preferably 65 to 80pbw, based on the weight of component B;

B2) a styrene-acrylonitrile graft copolymer modified polymer polyol having a functionality of 3 and a weight average molecular weight of 3000 to 9000g/mol, preferably 3500 to 8500g/mol, particularly preferably 4500 to 8000g/mol, in an amount of 0 to 40pbw, preferably 0 to 30pbw, particularly preferably 5 to 20pbw, based on the weight of component B.

6. Process according to claim 1 or 2, characterized in that component B further comprises at least one small chain extender of the alcohol, alkanolamine or diamine type in an amount of 0.5 to 3.5pbw, preferably 1 to 3pbw, particularly preferably 1.25 to 2.75pbw, based on the weight of component B.

7. A flexible high resilience polyurethane foam obtained by the process of any one of claims 1 to 6, which is prepared from a reaction system comprising:

component A isocyanate;

component B, comprising:

a polyol;

a foaming agent;

at least one amine catalyst; and

at least one amino-terminated long-chain extender having a functionality of 2 to 3, an ammonia number of 10 to 500mg KOH/g, preferably 20 to 450mg KOH/g, particularly preferably 28 to 350mg KOH/g (determined according to ASTM D2074-.

8. The foam of claim 7, wherein the amino-terminated long chain extender is present in an amount of 1 to 20pbw, preferably 1 to 17pbw, particularly preferably 2 to 15pbw, based on the weight of component B.

9. The foam of claim 7 wherein the amino terminated long chain extender is a polyetheramine.

10. A foam as claimed in any one of claims 7 to 9 wherein component A isocyanate comprises polymeric MDI, a mixture of MDI and TDI.

11. Foam according to any one of claims 7 to 9, wherein the polyol is selected from one or both of the following polyether polyols:

B1) a glycerol-initiated, EO-tipped long-chain polyether polyol having a functionality of 3 and a weight-average molecular weight of 4000 to 9000g/mol, preferably 4500 to 8500g/mol, particularly preferably 5000 to 8000g/mol (test method reference GB/T21863-2008), in an amount of 50 to 85pbw, preferably 60 to 85pbw, particularly preferably 65 to 80pbw, based on the weight of component B;

B2) a styrene-acrylonitrile graft copolymer modified polymer polyol having a functionality of 3 and a weight average molecular weight of 3000 to 9000g/mol, preferably 3500 to 8500g/mol, particularly preferably 4500 to 8000g/mol, in an amount of 0 to 40pbw, preferably 0 to 30pbw, particularly preferably 5 to 20pbw, based on the weight of component B.

12. Foam according to any one of claims 7 to 9, characterized in that component B further comprises at least one small chain extender of the alcohol, alkanolamine or diamine type in an amount of 0.5 to 3.5pbw, preferably 1 to 3pbw, particularly preferably 1.25 to 2.75pbw, based on the weight of component B.

13. Use of a polyurethane foam prepared by the method of any one of claims 1 to 7 in automotive seat back cushions and cushions.

14. A car seat back cushion or cushion comprising the polyurethane foam produced by the method of any one of claims 1 to 7.

Technical Field

The invention relates to a method for producing a flexible high-resilience polyurethane foam, to a polyurethane foam produced by said method, and to the use of said flexible high-resilience polyurethane foam in the production of cushions/cushions for motor vehicle seats.

Background

It is well known in the art that soft high resilience polyurethane foams are widely used in sofas, pillows, automotive interiors and automotive seat cushions, seat cushions and the like. However, with the rapid development of economy, the comfort requirements of people for automobiles and household articles are increasingly improved. Today, while there is a high standard for the physical properties of polyurethane products, the automotive industry is generally demanding polyurethane products with lower Volatile Organic Compounds (VOC), low fogging and low odor. However, amine catalysts are needed in the production process of polyurethane foam materials, and the amine catalysts with better performance such as bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine and dimethylimidazole have unpleasant ammonia odor, so that people who come into contact with the amine catalysts are uncomfortable and even the health of people is affected. Moreover, national automotive industry standards place increasingly stringent requirements on VOC emissions and unpleasant odors of flexible high resilience polyurethane foams for use in automotive seats.

Generally, organic volatiles and unpleasant odor of flexible high resilience polyurethane foam used for automobile seats are mainly derived from residual trace chemicals in isocyanate, polyether polyol, surfactant, catalyst, chain extender/cross-linker, which are raw materials for polyurethane production, and oxidation and thermal degradation products accompanying the occurrence of polyurethane reaction. In terms of main raw materials, major isocyanate and monomeric polyether production suppliers have invested in more optimized separation, purification equipment (activated carbon adsorption beds, ultra-high efficiency evaporators) at the factory production stage to achieve lower ppm levels of benzene-series (benzene, toluene, ethylbenzene, xylene, styrene) and aldehyde-series (formaldehyde, acetaldehyde, acrolein) volatile residues. Silicone surfactant manufacturers have also introduced high molecular weight, non-volatile surfactants that are produced using cleaner post-purification treatment processes. Polyurethane catalyst manufacturers have developed reactive polyurethane catalysts containing hydroxyl and/or amino substituent groups that can react with isocyanates to anchor them in the polyurethane macro-segment, thereby reducing the source of VOC and body odor from the polyurethane adjuvant itself. However, such reactive catalysts gradually deteriorate in catalytic and migratory properties during the chemical reaction of polyurethane, and thus require higher dosages. Still others in the art have tried to use highly reactive small molecule amine (-NH2) chain extenders/crosslinkers to coordinate with and even replace traditional small molecule diols/diols amines, triols/triolamines, to reduce the use of volatile and strong odor tertiary ammonia catalysts through the strong autocatalytic activity of the amine chain extenders/crosslinkers themselves. However, as the dosage of the small molecular amino chain extender/cross-linker increases, the hardness and the closed cell ratio of the foam are obviously increased. How to reduce odor remains a well-known problem in the industry.

CN104130371A discloses a low-odor high-resilience sponge for passenger car seats, which is prepared from a combined material and a black material according to the mass ratio of 100: 55-60, wherein the combined material comprises the following components in parts by weight: 50-80 parts of polyether polyol, 20-50 parts of grafted polyether, 0.2-0.3 part of amine catalyst, 0.2-0.5 part of early-stage gel catalyst, 0.5-0.7 part of later-stage gel catalyst, 3-4 parts of foaming agent, 1 part of cross-linking agent and 0.5-0.7 part of stabilizing agent; the invention also discloses the sponge for the passenger car seat with low odor and high resilience, which is prepared by adopting the black material with low odor and low toxicity and the polyether type combined material with low odor and low toxicity, the standard grade of the odor is 3.0 grade, the TVOC is 13.9ugC/g, and the sponge has the characteristics of low odor and high resilience and meets the requirements of people on the environmental protection performance and the mechanical property of the sponge for the passenger car seat.

US6051622A discloses a polyurethane foam for automobile seats, which is prepared from isocyanate group-terminated prepolymer prepared from isocyanate and polyol, chain extender and water.

US20130059145a1 discloses a polyurethane floor composed of 30% by weight of fibres, made from a system of isocyanate, water and polyol.

Despite the above disclosures, there is still a great need in the industry for flexible, high resilience polyurethane foams having short demold times, good resilience properties, and low odor.

Disclosure of Invention

In one aspect of the present invention, there is provided a process for preparing a flexible high resilience polyurethane foam by reacting a reaction system comprising:

component A isocyanate;

component B, comprising:

a polyol;

a foaming agent;

at least one amine catalyst; and

at least one amino-terminated long-chain extender having a functionality of 2 to 3, an ammonia number of 10 to 500mg KOH/g, preferably 20 to 450mg KOH/g, particularly preferably 28 to 350mg KOH/g (determined according to ASTM D2074-.

Preferably, the component a isocyanate comprises polymeric MDI, a mixture of MDI and TDI. The NCO content of the mixture is 20 to 48 wt.%, preferably 25 to 45 wt.%, particularly preferably 28 to 40 wt.%. The NCO content was determined by GB/T12009.4-2016. Preferably, the mass ratio of the polymeric MDI to the TDI is 1-55: 1-45: 5-80, and more preferably 1-55: 10-30: 20-80.

Preferably, in the process of the present invention the polyol is selected from one or both of the following polyether polyols:

B1) a glycerol-initiated, EO-tipped long-chain polyether polyol having a functionality of 3 and a weight-average molecular weight of 4000 to 9000g/mol, preferably 4500 to 8500g/mol, particularly preferably 5000 to 8000g/mol (test method reference GB/T21863-2008), in an amount of 50 to 85pbw, preferably 60 to 85pbw, particularly preferably 65 to 80pbw, based on the weight of component B;

B2) a polymer polyol having a functionality of 3 and a weight-average molecular weight of 3000 to 9000g/mol, preferably 3500 to 8500g/mol, particularly preferably 4500 to 8000g/mol (test methods are referred to GB/T21863-2008), modified by graft copolymerization of styrene and acrylonitrile, in an amount of 0 to 40pbw, preferably 0 to 30pbw, particularly preferably 5 to 20pbw, based on the weight of component B.

Preferably, the long chain extender is present in an amount of 1 to 20pbw, preferably 1 to 17pbw, particularly preferably 2 to 15pbw, based on the weight of component B.

Preferably, the long chain extender is a polyetheramine.

Preferably, component B comprises 2 to 5pbw, preferably 2.5 to 4.5pbw, particularly preferably 2.7 to 4pbw, of water based on the weight of component B.

In the process of the present invention, preferably, the component B further comprises a surfactant in an amount of 0.1 to 1pbw, preferably 0.25 to 0.9pbw, particularly preferably 0.35 to 0.8pbw, based on the weight of the component B.

In the method of the present invention, preferably, the component B further comprises at least one small molecule chain extender of alcohol, alcohol amine or diamine type, and the content of the small molecule chain extender is 0.5 to 3.5pbw, preferably 1 to 3pbw, and particularly preferably 1.25 to 2.75pbw, based on the weight of the component B.

The amine catalyst is preferably, but not limited to, one, two or more of triethylamine, tributylamine, dimethylethanolamine, bis (dimethylaminoethyl) ether, triethylenediamine, N-ethylmorpholine, N '-tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, dimethylaminopropylenediamine, N' -tetramethyldipropylenetriamine, or a mixture thereof, and a weak acid-modified product of the tertiary ammonia catalyst. In the process according to the invention, the reaction is preferably carried out in a mould, the polyurethane foam having a minimum demold time of < 4 minutes, preferably < 3.5 minutes.

In another aspect of the present invention, a flexible high resilience polyurethane foam is provided. The foam is prepared from a reaction system comprising the following components:

component A isocyanate;

component B, comprising:

a polyol;

a foaming agent;

at least one amine catalyst; and

at least one amino-terminated long-chain extender having a functionality of 2 to 3, an ammonia number of 10 to 500mg KOH/g, preferably 20 to 450mg KOH/g, particularly preferably 28 to 350mg KOH/g (determined according to ASTM D2074-.

Preferably, the component a isocyanate comprises polymeric MDI, a mixture of MDI and TDI. The NCO content of the mixture is 20 to 48 wt.%, preferably 25 to 45 wt.%, particularly preferably 28 to 40 wt.%. The NCO content was determined by GB/T12009.4-2016. Preferably, the mass ratio of the polymeric MDI to the TDI is 1-55: 1-45: 5-80, and more preferably 1-55: 10-30: 20-80.

Preferably, the polyol is selected from one or two of the following polyether polyols:

B1) a glycerol-initiated, EO-tipped long-chain polyether polyol having a functionality of 3 and a weight-average molecular weight of 4000 to 9000g/mol, preferably 4500 to 8500g/mol, particularly preferably 5000 to 8000g/mol (test method reference GB/T21863-2008), in an amount of 50 to 85pbw, preferably 60 to 85pbw, particularly preferably 65 to 80pbw, based on the weight of component B;

B2) a polymer polyol having a functionality of 3 and a weight-average molecular weight of 3000 to 9000g/mol, preferably 3500 to 8500g/mol, particularly preferably 4500 to 8000g/mol (test methods are referred to GB/T21863-2008), modified by graft copolymerization of styrene and acrylonitrile, in an amount of 0 to 40pbw, preferably 0 to 30pbw, particularly preferably 5 to 20pbw, based on the weight of component B.

Preferably, the EO content of the long-chain polyether polyol is 5 to 75 wt%, preferably 5 to 50 wt%, particularly preferably 10 to 20 wt%, based on the weight of the long-chain polyether polyol.

The polyurethane foam of the present invention preferably contains 1 to 20pbw, preferably 1 to 17pbw, particularly preferably 2 to 15pbw, of the amino-terminated long chain extender based on the weight of component B.

In the polyurethane foam of the present invention, preferably, the amino terminated long chain extender is polyether amine.

The polyurethane foam of the present invention preferably comprises from 2 to 5pbw, preferably from 2.5 to 4.5pbw, particularly preferably from 2.7 to 4pbw, of water based on the weight of component B.

The amine catalyst is preferably, but not limited to, one, two or more of triethylamine, tributylamine, dimethylethanolamine, bis (dimethylaminoethyl) ether, triethylenediamine, N-ethylmorpholine, N '-tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, dimethylaminopropylenediamine, N' -tetramethyldipropylenetriamine, or a mixture thereof, and a weak acid-modified product of the tertiary ammonia catalyst.

The polyurethane reaction system of the present invention preferably further comprises a surfactant in an amount of 0.1 to 1pbw, preferably 0.25 to 0.9pbw, and particularly preferably 0.35 to 0.8pbw, based on the weight of component B.

In the polyurethane reaction system of the present invention, preferably, the component B further includes at least one alcohol, alcohol amine or diamine small molecule chain extender, and the content of the small molecule chain extender is 0.5 to 3.5pbw, preferably 1 to 3pbw, and particularly preferably 1.25 to 2.75pbw, based on the weight of the component B.

The polyurethane foams of the present invention preferably have a demold time of < 4 minutes, preferably < 3.5 minutes.

The polyurethane foam of the present invention preferably has a density of 45 to 75kg/m³More preferably 45 to 55 kg/m³。

The falling ball rebound resilience of the polyurethane foam of the present invention is preferably 55% or more.

Through experiments, the invention unexpectedly discovers that the polyurethane foam prepared from the amino-terminated long-chain extender used in the invention and the components such as polyether polyol, catalyst, foaming agent and the like matched with the amino-terminated long-chain extender has the advantages of short demolding time, excellent physical properties (such as good elasticity and high comfort level) and satisfactory low odor.

The soft high-resilience polyurethane foam can be widely applied to the fields of automobile decoration and daily household, and comprises but is not limited to automobile seat cushions/back cushions, sofas, mattresses, pillows, office chair cushions and the like.

In a further aspect, the present invention provides the use of the flexible high resilience polyurethane foam of the present invention in a back cushion or a seat cushion of an automobile seat.

In still another aspect of the present invention, there is provided a back cushion or a seat cushion for an automobile seat, comprising the above soft high resilience polyurethane foam.

Detailed Description

The following terms used in the present invention have the following definitions or explanations.

pbw refers to the mass parts of each component of the polyurethane reaction system;

functionality, means according to the industry formula: a functionality of hydroxyl value (Mw/56100); wherein, the molecular weight is measured by GPC high performance liquid chromatography, and the test method is referred to GB/T21863-2008.

Components of polyurethane foam reaction system

A) Polyisocyanates

Any organic polyisocyanate may be used in the preparation of the flexible high resilience polyurethane foam of the present invention, including aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. The polyisocyanate can be represented by the general formula R (NCO) n, wherein R represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, an araliphatic hydrocarbon group having 8 to 15 carbon atoms, and n is 2 to 4.

Useful polyisocyanates include, preferably but are not limited to, vinyl diisocyanate, tetramethylene 1, 4-diisocyanate, Hexamethylene Diisocyanate (HDI), dodecyl 1, 2-diisocyanate, cyclobutane 1, 3-diisocyanate, cyclohexane 1, 4-diisocyanate, 1-isocyanato 3, 3, 5-trimethyl 5-isocyanatomethylcyclohexane, hexahydrotoluene 2, 4-diisocyanate, hexahydrophenyl 1, 3-diisocyanate, hexahydrophenyl 1, 4-diisocyanate, perhydrogenated diphenylmethane 2, 4-diisocyanate, perhydrogenated diphenylmethane 4, 4-diisocyanate, phenylene 1, 3-diisocyanate, phenylene 1, 4-diisocyanate, stilbene 1, 4-diisocyanate, 3-dimethyl-4, 4-diphenyldiisocyanate, toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate (TDI), diphenylmethane-2, 4 ' -diisocyanate (MDI), diphenylmethane-2, 2 ' -diisocyanate (MDI), diphenylmethane-4, 4 ' -diisocyanate (MDI), mixtures of diphenylmethane diisocyanates and/or homologues of diphenylmethane diisocyanates having more rings, polyphenylmethane polyisocyanates (polymeric MDI), naphthylene-1, 5-diisocyanate (NDI), their isomers, any mixtures thereof with their isomers.

Useful polyisocyanates also include isocyanates modified with a carbonized diamine, allophanate or isocyanate, preferably, but not limited to, diphenylmethane diisocyanate, carbonized diamine modified diphenylmethane diisocyanate, isomers thereof, mixtures thereof with isomers thereof.

When used in the present invention, the polyisocyanate includes an isocyanate dimer, trimer, tetramer or a combination thereof.

In a preferred embodiment of the invention, the isocyanate comprises polymeric MDI, a mixture of MDI and TDI. The NCO content of the mixture is 20 to 48 wt.%, preferably 25 to 45 wt.%, particularly preferably 28 to 40 wt.%. The NCO content was determined by GB/T12009.4-2016.

Preferably, the mass ratio of the polymeric MDI to the TDI is 1-55: 1-45: 5-80, and more preferably 1-55: 10-30: 20-80.

B) Polyhydric alcohols

The polyol of the present invention may be a polyether polyol, a polyester polyol, a polycarbonate polyol and/or mixtures thereof.

The polyol of the present invention is preferably one or more polyether polyols, wherein at least one polyether polyol is a polyether polyol having a polyfunctional small molecule alcohol as an initiator. The polyether polyol has a functionality of 2 to 8, preferably 3 to 6, and a hydroxyl value of 20 to 1200KOH/g, preferably 20 to 800 mgKOH/g.

The polyether polyols may be prepared by known processes. Ethylene oxide or propylene oxide is typically prepared with ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, triethanolamine, toluenediamine, sorbitol, sucrose, or any combination thereof as a starter.

In addition, the polyether polyol can be prepared by reacting at least one alkylene oxide containing 2 to 4 carbon atoms with a compound containing 2 to 8, preferably, but not limited to, 3 to 6 active hydrogen atoms or other reactive compounds in the presence of a catalyst.

Examples of such catalysts are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, or alkali metal alkoxides such as sodium methoxide, sodium ethoxide or potassium isopropoxide.

Useful olefin oxides include, preferably but are not limited to, tetrahydrofuran, ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, styrene oxide, and any mixtures thereof.

Useful active hydrogen atom containing compounds include polyhydroxy compounds, preferably, but not limited to, water, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, trimethylolpropane, any mixture thereof, more preferably polyhydric, especially trihydric or higher alcohols, such as glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose. Useful active hydrogen atom-containing compounds also include, preferably but not limited to, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, or aromatic or aliphatic substituted diamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine or toluenediamine.

Other reactive compounds that may be used include ethanolamine, diethanolamine, methylethanolamine, ethylethanolamine, methyldiethanolamine, ethyldiethanolamine, triethanolamine, and ammonia.

The polyether polyol prepared by using amine as a starter comprises a compound obtained by reacting amine as a starter with an alkylene oxide compound.

The term "alkylene oxide compound" as used in the present invention generally refers to compounds having the following general formula (I):

wherein R is₁And R₂Independently selected from H, C₁～C₆Straight and branched chain alkyl groups as well as phenyl and substituted phenyl groups.

Preferably, the first and second liquid crystal materials are,R₁and R₂Independently selected from H, methyl, ethyl, propyl and phenyl.

The person skilled in the art knows the preparation of "alkylene oxide compounds", which can be obtained, for example, by oxidation of alkylene compounds.

Examples of the alkylene oxide compounds useful in the present invention include, but are not limited to: ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, styrene oxide or mixtures thereof, with mixtures of ethylene oxide and 1, 2-propylene oxide being particularly preferred.

The term "alkylene oxide compound" as used in the present invention also includes oxacycloalkanes, examples of which include, but are not limited to: tetrahydrofuran and oxetane.

As used herein, the term "amine" refers to a compound containing a primary amino group, a secondary amino group, a tertiary amino group, or a combination thereof. Examples of compounds useful as amines in the present invention include, but are not limited to, triethanolamine, ethylenediamine, tolylenediamine, diethylenetriamine, triethylenetetramine, and derivatives thereof, preferably ethylenediamine, tolylenediamine, and particularly preferably tolylenediamine.

Preferably, the polyether polyols of the present invention comprise long-chain polyether polyols having a functionality of 3, a glycerol-initiated, EO-capped, weight average molecular weight of 4000 to 9000g/mol, preferably 4500 to 8500g/mol, particularly preferably 5000 to 8000g/mol, in an amount of 50 to 85pbw, preferably 60 to 85pbw, particularly preferably 65 to 80pbw, based on the weight of component B. The EO content of the long-chain polyether polyol is 5-75 wt%, preferably 5-50 wt%, and particularly preferably 10-20 wt%.

Preferably, the polyols of the invention also include styrene-acrylonitrile graft copolymer-modified polymer polyols having a functionality of 3 and a weight-average molecular weight of from 3000 to 9000g/mol, preferably from 3500 to 8500g/mol, particularly preferably from 4500 to 8000g/mol, in an amount of from 0 to 40pbw, preferably from 0 to 30pbw, particularly preferably from 5 to 20pbw, based on the weight of component B.

The vinyl polymer grafted Polyether Polyol is commonly called 'polymer Polyol' (Polyether Polyol) Or Polyether (POP) polymer Polyol, and is prepared by taking general Polyether Polyol as basic Polyether (general soft foam Polyether triol and high-activity Polyether), adding vinyl monomers such as acrylonitrile and/or styrene, methyl methacrylate, vinyl acetate, vinyl chloride and the like and an initiator, and carrying out free radical graft polymerization at about 100 ℃ under the protection of nitrogen.

The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, aliphatic carboxylic acid containing 2 to 12 carbon atoms, such as: succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanecarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, mixtures thereof. The dibasic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and mixtures thereof. The polyhydric alcohol is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, dipropylene glycol, 1, 3-methylpropylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone is preferably, but not limited to, a polyester polyol prepared from epsilon-caprolactone.

The polycarbonate polyol is preferably, but not limited to, a polycarbonate diol. The polycarbonate diols may be prepared by reacting diols with dialkyl or diaryl carbonates or phosgene. The diol is preferably, but not limited to, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.

Foaming agent

The foaming agent of the present invention may be selected from various physical foaming agents or chemical foaming agents.

Useful blowing agents include water, halogenated hydrocarbons, and the like. Useful halohydrocarbons are preferably pentafluorobutane, pentafluoropropane, chlorotrifluoropropene, hexafluorobutene, HCFC-141 b (monofluorodichloroethane), HFC-365 mfc (pentafluorobutane), HFC-245 fa (pentafluoropropane), or any mixture thereof. Useful hydrocarbon compounds include preferably butane, pentane, Cyclopentane (CP), hexane, cyclohexane, heptane and any mixture thereof.

The blowing agent of the invention is preferably water in an amount of from 2 to 5pbw, preferably from 2.5 to 4.5pbw, particularly preferably from 2.7 to 4pbw, based on the weight of component B.

Catalyst and process for preparing same

The catalyst of the present invention is preferably an amine catalyst. The amine catalyst includes, but is not limited to, one, two or more of triethylamine, tributylamine, dimethylethanolamine, bis (dimethylaminoethyl) ether, triethylenediamine, N-ethylmorpholine, N '-tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, dimethylaminopropylenediamine, N' -tetramethyldipropylenetriamine, and weak acid-modified products of the amine catalyst. The catalyst content of the present invention is preferably 0.20 to 4.00 pbw.

Surface active agent

In an embodiment of the present invention, the polyurethane reaction system of the present invention further comprises a surfactant, preferably, but not limited to, an ethylene oxide derivative of siloxane. The surfactant is present in an amount of 0.1 to 1pbw, preferably 0.25 to 0.9pbw, particularly preferably 0.35 to 0.8 pbw.

Chain extender

The chain extender used in the present invention is selected from multifunctional alcohols or amines containing hydroxyl or amino and having low molecular weight, and the commonly used alcohol chain extenders include 1, 4-Butanediol (BDO), 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sorbitol, Diethylaminoethanol (DEAE), etc. The amine chain extender includes MOCA, liquid MOCA modified with formaldehyde, Ethylenediamine (EDA), N-dihydroxy (diisopropyl) aniline (HPA), etc. And hydroquinone di (. beta. -hydroxyethyl) ether (HQEE). As is well known to those skilled in the art, chain extenders commonly used in the polyurethane art are small molecule alcohols containing di-or poly-hydroxyl groups, amino, imino or ether alcohols; long chain extenders, particularly amino terminated long chain extenders, have not been tried.

The polyurethane reaction system of the present invention includes at least one amino terminated long chain extender. The long chain extender has a functionality of 2-3, an ammonia value of 10-500 mg KOH/g, preferably 20-450 mg KOH/g, particularly preferably 28-350 mg KOH/g (tested according to ASTM D2074-.

In the polyurethane reaction system of the present invention, preferably, the content of the long chain extender is 1 to 20pbw, preferably 1 to 17pbw, and particularly preferably 2 to 15pbw, based on the weight of the component B.

In the polyurethane reaction system of the present invention, preferably, the long-chain extender is polyether amine.

Polyetheramines (Amine-Terminated Polyether, abbreviated to ATPE) are a class of polyolefin compounds having a flexible Polyether backbone, Terminated by primary or secondary Amine groups. The basic structure contains at least one polyalkylene glycol function, which is critical for its properties. The polyalkylene glycols increase the water solubility of the polyetheramines. The melting point and the viscosity of the polyetheramine are also influenced. The structural changes include polyoxyethylene diamine, polyoxypropylene diamine, polyoxyethylene/oxypropylene diamine, polyoxypropylene triamine, polytetramethylene ether diamine, etc. Most of these compounds are obtained by chemical treatment of the terminal hydroxyl groups, starting from the corresponding polyether polyols. The structure of the hydrocarbon group connected with the terminal amino group can be divided into aromatic and aliphatic groups. The polymer is light yellow or colorless transparent liquid at room temperature, has the advantages of low viscosity, low vapor pressure, high primary amine content and the like, can be dissolved in solvents such as ethanol, aliphatic hydrocarbons, aromatic hydrocarbons, esters, glycol ethers, ketones, water and the like, and is a polymer with a main chain of a polyether structure and active functional groups at the tail end of an amino group. The polyetheramines are obtained by amination of polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers at elevated temperature and pressure. By selecting different polyoxyalkyl structures, a series of properties such as reactivity, toughness, viscosity and hydrophilicity of the polyether amine can be adjusted, and the amine group provides possibility for the polyether amine to react with various compounds.

The polyether amine can be used as a high-performance curing agent of epoxy resin, and is used for producing high-strength and high-toughness composite materials, coatings, ornaments, cleaning agents and the like. It is well known to those skilled in the art that in the field of polyurethane polyurea elastomers, polyetheramines are involved in the polymerization as the main starting material. But have not been used as curing agents or chain extenders in flexible, high resilience polyurethane foam blowing systems.

In industrial production, polyetheramines can generally be prepared by ammonolysis and leaving group processes. The synthesis process of the polyether amine comprises a batch process and a continuous process. It is well known in the art that the production process adopted by Huntsman corporation is a continuous fixed bed process, and polyetheramine is catalytically synthesized by using a metal catalyst supported on a carrier.

The polyurethane reaction system of the present invention preferably further comprises an alcohol, alcohol amine or diamine small molecule chain extender, such as one, two or more of 1, 4-BD, DEOA, TEOA and DETDA, and the content of the small molecule chain extender is 0.5 to 3.5pbw, preferably 1 to 3pbw, particularly preferably 1.25 to 2.75pbw, based on the weight of the component B.

The polyurethane foam of the present invention preferably has a density of 45 to 75kg/m³More preferably 45 to 55 kg/m³。

The falling ball rebound resilience of the polyurethane foam of the present invention is preferably 55% or more.

Through experiments, the unexpected discovery shows that the polyurethane foam prepared by the reaction system containing the long-chain extender and the isocyanate, the polyether glycol, the catalyst, the foaming agent and the like matched with the long-chain extender reduces the demoulding time and improves the production efficiency; on the other hand, the excellent physical properties of the flexible high resilience polyurethane foam are maintained, such as: good elasticity and comfort, while also reducing odor.

Method for preparing soft high-resilience polyurethane foam

The method is to react a reaction system comprising the following components to prepare the polyurethane foam:

component A isocyanate;

component B, comprising:

a polyol;

a foaming agent;

at least one amine catalyst; and

at least one amino-terminated long-chain extender having a functionality of 2 to 3, an ammonia number of 10 to 500mg KOH/g, preferably 20 to 450mg KOH/g, particularly preferably 28 to 350mg KOH/g (determined according to ASTM D2074-.

Preferably, in the process of the present invention the polyol is selected from one or both of the following polyether polyols:

B1) a glycerol-initiated, EO-tipped long-chain polyether polyol having a functionality of 3 and a weight-average molecular weight of 4000 to 9000g/mol, preferably 4500 to 8500g/mol, particularly preferably 5000 to 8000g/mol (test method reference GB/T21863-2008), in an amount of 50 to 85pbw, preferably 60 to 85pbw, particularly preferably 65 to 80pbw, based on the weight of component B;

B2) a polymer polyol having a functionality of 3 and a weight-average molecular weight of 3000 to 9000g/mol, preferably 3500 to 8500g/mol, particularly preferably 4500 to 8000g/mol (test methods are referred to GB/T21863-2008), modified by graft copolymerization of styrene and acrylonitrile, in an amount of 0 to 40pbw, preferably 0 to 30pbw, particularly preferably 5 to 20pbw, based on the weight of component B.

Preferably, the long chain extender is present in an amount of 1 to 20pbw, preferably 1 to 17pbw, particularly preferably 2 to 15pbw, based on the weight of component B.

Preferably, the long chain extender is a polyetheramine.

Preferably, component B comprises 2 to 5pbw, preferably 2.5 to 4.5pbw, particularly preferably 2.7 to 4pbw, of water based on the weight of component B.

In the process of the present invention, preferably, the component B further comprises a surfactant in an amount of 0.1 to 1pbw, preferably 0.25 to 0.9pbw, particularly preferably 0.35 to 0.8pbw, based on the weight of the component B.

In the method of the present invention, preferably, the component B further comprises at least one small molecule chain extender of alcohol, alcohol amine or diamine type, and the content of the small molecule chain extender is 0.5 to 3.5pbw, preferably 1 to 3pbw, and particularly preferably 1.25 to 2.75pbw, based on the weight of the component B.

In the process according to the invention, the reaction is preferably carried out in a mould, the polyurethane foam having a minimum demold time of < 4 minutes, preferably < 3.5 minutes.

The flexible high resilience polyurethane foam of the present invention can be prepared using methods well known in the art. In one embodiment of the invention, the reaction components are mixed by a mixing head or in a mixing chamber. The reaction mixture is then applied to a suitable closed mold and the foam expands to form a closed mold sized foam.

The flexible, high resilience polyurethane foams of the present invention may also be prepared by a molded foam process. The molded foam process generally employs a one-shot process in which the isocyanate component and the isocyanate-reactive component are mixed and injected into a mold, the mold is closed, and the foam expands to fill the mold to form a flexible, high resilience polyurethane foam having the shape and size of the mold. The minimum demolding time for demolding is < 4 minutes, preferably < 3.5 minutes.

Application of soft high-resilience polyurethane foam in preparation of automobile seat cushion and back cushion

The invention also provides application of the soft high-resilience polyurethane foam in preparation of a cushion and a back cushion of an automobile seat.

Cushion and back cushion for automobile seat

The automobile seat of the present invention comprises the above soft high resilience polyurethane foam.