CN116239748A

CN116239748A - Polyol composition

Info

Publication number: CN116239748A
Application number: CN202111495131.8A
Authority: CN
Inventors: 施灵; 卢骅; 纪南纱子
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2021-12-08
Filing date: 2021-12-08
Publication date: 2023-06-09

Abstract

The invention relates to a polyol composition, a corresponding polyurethane reaction system and a polyurethane foam prepared by the same.

Description

Polyol composition

Technical Field

The invention relates to a polyol composition, a polyurethane reaction system and polyurethane foam prepared by the same.

Background

Polyurethane foams are known in the art to be useful in the manufacture of automotive interiors, such as headliners, pillar trim sandwich structures, and the like. However, with the rapid development of economy, people have increasingly demanded comfort for automobiles and household articles. Nowadays, the automotive industry has a higher standard for the physical properties of polyurethane products, while requiring lower VOC emissions, low fogging and low odor. However, the automotive industry has a very long approval cycle for raw materials, and often new raw materials are difficult to accept. How to economically, effectively and environmentally improve the quality and the applicability of polyurethane raw materials is a difficult problem to be solved.

CN1098298C discloses a process for preparing flexible polyurethane foam by reacting a polyisocyanate and two different polyols under foam forming conditions to prepare a rigid foam and then extruding the obtained rigid foam.

CN1257203C discloses a process for preparing a viscoelastic polyurethane foam by reacting a polyisocyanate composition with a polyol composition comprising b 1) an EO-rich polyol; b2 Polyols having an EO content of between 20-50% and a primary hydroxyl content of at least 50%; b3 Polyols having an EO content of between 10-20% and a primary hydroxyl content of at least 50%; and b 4) polyoxyalkylene glycol.

Despite the above disclosures, there remains a great need in the marketplace for optimized polyol compositions.

Disclosure of Invention

In one aspect of the present invention, there is provided a polyol composition comprising:

b1 A functionality of 2 to 4, preferably 3, (more preferably glycerol, sucrose and/or sorbitol-initiated), a weight average molecular weight of 4000 to 7000g/mol (test methods see GBT 21863-2008), preferably 4500 to 5000g/mol, based on the total weight of B1) EO content of 12.0% by weight, preferably 13.0% by weight, particularly preferably 14.0 to 25.0% by weight of EO-and/or PO-capped polyether polyol;

b2 A functionality of 1.5 to 3, preferably 2, (more preferably propylene glycol initiated), a weight average molecular weight of 600 to 1200g/mol (test methods see GBT 21863-2008), preferably 800 to 1100g/mol, a PO-terminated polyether polyol;

b3 A functionality of 1.5 to 3, preferably 2, (more preferably ethylene glycol initiated), a weight average molecular weight of 100 to 400g/mol (test methods see GBT 21863-2008), preferably 150 to 250g/mol, EO-capped polyether polyol having an EO content of 1 to 15% by weight, preferably 1 to 12% by weight, based on the total weight of B3);

b4 A functionality of 2 to 4, preferably 3, (more preferably glycerol-initiated), a weight average molecular weight of 4000 to 6000g/mol (test methods see GBT 21863-2008), preferably 4000 to 5000g/mol, based on the total weight of the B4) component, EO content of not less than 50.0wt%, preferably not less than 70.0wt%, PO and/or EO-capped polyether polyol.

Wherein the content ratio of the components B3) and B4) is B3): b4 And) 1, preferably 0.5, more preferably 0.1-0.45.

Preferably, the content of B1) is from 20 to 60% by weight, preferably from 30 to 60% by weight, based on the total weight of the polyol composition.

Preferably, the content of said B2) is from 10 to 50wt%, preferably from 15 to 40wt%, based on the total weight of the polyol composition.

Optionally, the content of B3) is from 1 to 15wt%, preferably from 1 to 10wt%, based on the total weight of the polyol composition.

Preferably, the content of said B4) is from 5 to 25wt%, preferably from 10 to 20wt%, more preferably from 13 to 15wt%, based on the total weight of the polyol composition.

Preferably, the polyol composition further comprises B5) at least one surfactant.

Preferably, the polyol composition further comprises B6) at least one blowing agent.

Preferably, the blowing agent is selected from water in an amount of 5 to 20wt%, preferably 10 to 15wt%, based on the total weight of the polyol composition.

Preferably, the polyol composition further comprises B7) at least one catalyst.

Preferably, the difference between the foam time and the gel time of the polyurethane reaction system comprising the polyol composition, i.e. the difference between the foam time minus the gel time is > 20 seconds, preferably > 25 seconds, more preferably 25-50 seconds.

Preferably, the absolute value of the 24 hour shrinkage of the polyurethane foam produced from the polyol composition is 10% or less, preferably 2% or less (test method GB 8811-2008).

Preferably, the polyol composition comprising B3) and B4) yields a polyurethane foam having an absolute reduction in 24-hour shrinkage of not less than 5%, preferably not less than 10%, compared to a polyol composition not comprising B3) and B4) (test method GB 8811-2008).

Preferably, and without B3): b4 Compared to the polyol composition of < 1), the composition comprising B3): b4 A polyol composition of < 1 (preferably < 0.5, more preferably 0.1 to 0.45) gives a polyurethane foam having an absolute 24-hour reduction of not less than 5%, preferably not less than 10% (test method GB 8811-2008). Specifically, if B3) is included: b4 A polyol composition of & lt 1) gives a polyurethane foam having an absolute value of 24-hour shrinkage of X excluding B3): b4 The 24-hour shrinkage of the polyurethane foam produced from the polyol composition of < 1 is Y, then the composition comprises B3): b4 The absolute value of 24-hour shrinkage reduction of the polyurethane foam produced from the polyol composition of < 1 was (Y-X)/Y100%.

Preferably, and excluding said B3): b4 Compared to the polyurethane reaction system of the polyol composition of < 1 (preferably < 0.5, more preferably 0.1-0.45), said composition comprising B3): b4 The difference between the foam-spitting time and the gel time of the polyurethane reaction system of the polyol composition of & lt 1 is increased by not less than 10%, preferably not less than 15%. Specifically, if B3) is included: b4 A difference between the foam-releasing time and the gel time of the polyurethane reaction system of the polyol composition of & lt 1 is P excluding B3): b4 A difference between the foam-spitting time and the gel time of the polyurethane reaction system of the polyol composition of & lt 1 is Q, said composition comprising B3): b4 The difference between the foam-releasing time and the gel time of the polyurethane reaction system of the polyol composition of (P-Q)/Q.ANGSTROM.100%.

Surprisingly, the polyol composition comprising the components B3) and B4) and the components B1) and B2) which are matched with the polyol composition can prepare polyurethane foam with ideal uniform open cells, low density and higher stability, and simultaneously, the process is more stable and efficient, foam collapse and shrinkage are not easy to occur, the yield is greatly improved, and the production efficiency is improved. Moreover, the waste of raw materials is avoided, the cost is saved, and the method is more environment-friendly.

In particular, the polyol compositions of the invention comprising specific amounts of the components, in particular the ratio by weight of B3) to B4), of < 1 (preferably < 0.5, more preferably from 0.1 to 0.45), have satisfactory manufacturability and enable simple, economical and efficient production of more stable, low-density polyurethane foams with > 50% by volume open cells, which better meet specific applications.

In another aspect of the present invention, there is provided a polyurethane reaction system comprising:

component A, polyisocyanate;

component B, comprising: the polyol composition of the present invention as described previously.

Preferably, the component a comprises:

a1 0 to 10% by weight, preferably 0.1 to 8% by weight, based on the total weight of component A, of 2,2' -diphenylmethane diisocyanate;

a2 10 to 30% by weight, preferably 15 to 25% by weight, based on the total weight of component A, of 2,4' -diphenylmethane diisocyanate; and

a3 25 to 75% by weight, preferably 35 to 55% by weight, based on the total weight of component A, of 4,4' -diphenylmethane diisocyanate.

Preferably, the polyurethane reaction system further comprises component C) expanded graphite.

Preferably, the mass ratio of the component A to the component B is 150-180:100, preferably 165-175:100.

Preferably, the mass ratio of the component A to the component B to the component C is 150-180:100:15-35, preferably 165-175:100:15-25.

Preferably, the difference between the foam-releasing time and the gel time of the polyurethane reaction system is more than 20 seconds, preferably more than or equal to 25 seconds, more preferably 25-50 seconds.

Preferably, and excluding said B3): b4 Compared to a polyurethane reaction system of < 1), the polyurethane reaction system comprises B3): b4 The difference between the foam-discharging time and the gel time of the polyurethane reaction system less than 1 is increased by more than or equal to 10 percent, preferably more than or equal to 15 percent.

The polyurethane reaction system of the present invention comprising the aforementioned polyol composition can produce satisfactory polyurethane foams and related polyurethane products.

In yet another aspect, the present invention provides a polyurethane foam prepared by reacting the polyurethane reaction system of the present invention.

Preferably, the absolute value of the 24-hour shrinkage of the polyurethane foam is 10% or less, preferably 2% or less (test method GB 8811-2008).

Preferably, and without B3): b4 Compared to polyurethane foam made from the polyol composition of < 1, the composition comprises B3): b4 The absolute 24-hour shrinkage of the polyurethane foam produced from the polyol composition of < 1 is reduced by 5% or more, preferably 10% or more (test method GB 8811-2008).

Preferably, the polyurethane foam has a core density of 10 to 16Kg/m3, preferably 10 to 15Kg/m3 (test method ASTM D1622-03).

Optionally, the polyurethane foam has > 50% by volume open cells (measured according to DIN ISO 4590-86).

In still another aspect of the present invention, there is provided a method for preparing a polyurethane foam by reacting the aforementioned polyurethane reaction system.

In yet another aspect of the present invention, there is provided a polyurethane composite panel comprising two facings and a rigid polyurethane foam layer positioned between the two facings, wherein the rigid polyurethane foam is produced by the method of the present invention for producing a polyurethane foam.

Preferably, the two facing materials are each selected from the group consisting of glass fibers, natural fibers, paper, thermoplastic films, and nonwoven fabrics.

In yet another aspect of the present invention, there is provided a method for preparing the polyurethane composite panel of the present invention, comprising the steps of:

coating adhesives on the inner surfaces of the two prepared surface layers or the surfaces of the polyurethane foam layers, placing the polyurethane foam between the two surface layers, then placing the polyurethane foam in a mold, and closing the mold for 30-50 seconds at the temperature of 100-150 ℃ to obtain the polyurethane composite board.

In a further aspect of the invention there is provided the use of the polyurethane foam of the invention for the manufacture of automotive interiors, preferably for automotive engine compartment insulation pads.

In yet another aspect of the invention, there is provided a polyurethane product comprising the polyurethane foam of the invention.

Preferably, the polyurethane product is selected from automotive interiors, preferably automotive engine compartment insulation mats.

Detailed description of the preferred embodiments

Various aspects of the invention will now be described in detail.

The invention provides a polyol composition, a corresponding polyurethane reaction system, polyurethane foam prepared by the polyol composition and the polyurethane reaction system. The polyol composition includes:

b1 Glycerol, sucrose and/or sorbitol-initiated polyether polyols having a weight average molecular weight of 4000 to 7000g/mol (test methods see GBT 21863-2008), preferably 4500 to 5000g/mol, EO content of 12.0% by weight or more, preferably 13.0% by weight or more, particularly preferably 14.0 to 25.0% by weight or more, based on the total weight of B1), EO and/or PO-capped polyether polyols;

b2 Propylene glycol-initiated, weight average molecular weight of 600-1200g/mol (test methods see GBT 21863-2008), preferably 800-1100g/mol, PO-terminated polyether polyol;

b3 Ethylene glycol-initiated, weight average molecular weight of 100-400g/mol (test methods refer to GBT 21863-2008), preferably 150-250g/mol, EO-capped polyether polyols having EO content of 1-15% by weight, preferably 1-12% by weight, based on the total weight of B3);

b4 Glycerol-initiated, weight-average molecular weights of 4000 to 6000g/mol (test methods see GBT 21863-2008), preferably 4000 to 5000g/mol, PO and/or EO-capped polyether polyols, wherein the EO content is > 50.0% by weight, preferably > 70.0% by weight, based on the total weight of the B4) component.

Polyhydric alcohol

Polyols useful in the present invention include a variety of polyether polyols and/or mixtures thereof.

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

In addition, the polyether polyols may also 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 8 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, but are not limited to, preferably 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-propanediol, 1, 3-propanediol, diethylene glycol, trimethylolpropane, any mixtures thereof, more preferably polyhydric, especially ternary or higher alcohols such as glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose. Useful active hydrogen atom-containing compounds also include, preferably but are 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.

Examples of 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, particularly preferably mixtures of ethylene oxide with 1, 2-propylene oxide.

As used herein, the term "alkylene oxide" also includes oxygenated hydrocarbons, examples of which include, but are not limited to: tetrahydrofuran and oxetane.

When used in the present invention, 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 the amine compound usable as the present invention include, but are not limited to, triethanolamine, ethylenediamine, toluenediamine, diethylenetriamine, triethylenetetramine and their derivatives, preferably ethylenediamine, toluenediamine, particularly preferably toluenediamine.

Polyisocyanate component

The isocyanate useful in the present invention may include any organic polyisocyanate including aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. The polyisocyanate may 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=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, 5-trimethyl-5-isocyanatomethyl cyclohexane, hexahydrotoluene 2, 4-diisocyanate, hexahydrophenyl 1, 3-diisocyanate, hexahydrophenyl 1, 4-diisocyanate, perhydro-diphenylmethane 2, 4-diisocyanate, perhydro-diphenylmethane 4, 4-diisocyanate, phenylene 1, 3-diisocyanate, phenylene 1, 4-diisocyanate, stilbene 1, 4-diisocyanate, 3-dimethyl 4, 4-diphenyl diisocyanate, toluene 2, 4-diisocyanate (TDI), toluene 2, 6-diisocyanate (TDI), diphenylmethane 2,4' -diisocyanate (MDI), diphenylmethane 2,4' -diisocyanate, diphenylmethane diisocyanate (MDI), diphenylmethane 4' -diisocyanate, diphenylmethane diisocyanate, polymeric polyisocyanates having the same or a mixture of more of diphenylmethane and diphenylmethane polyisocyanates (MDI), naphthalene-1, 5-diisocyanate (NDI), their isomers, any mixtures thereof with their isomers.

Useful polyisocyanates may also include isocyanates modified with diamines, allophanates, or isocyanates, preferably but not limited to diphenylmethane diisocyanate, diamine-modified diphenylmethane diisocyanate, isomers thereof, and mixtures thereof with isomers thereof.

When used in the present invention, the polyisocyanate may comprise an isocyanate dimer, trimer, tetramer, or combinations thereof.

Preferably, the polyisocyanate component comprises: a1 0 to 10% by weight, preferably 0.1 to 8% by weight, based on the total weight of component A, of 2,2' -diphenylmethane diisocyanate; a2 0 to 30% by weight, preferably 10 to 25% by weight, based on the total weight of component A, of 2,4' -diphenylmethane diisocyanate; and A3) from 25 to 75% by weight, preferably from 35 to 55% by weight, based on the total weight of component A, of 4,4' -diphenylmethane diisocyanate.

The NCO content of the organic polyisocyanates according to the invention is 20 to 33% by weight, preferably 25 to 32% by weight, particularly preferably 30 to 32% by weight. NCO content was determined by GB/T12009.4-2016.

The organic polyisocyanates can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers may be obtained by reacting an excess of the above organic polyisocyanate with a compound having at least two isocyanate reactive groups at a temperature of, for example, 30 to 100 ℃, preferably about 80 ℃. The NCO content of the polyisocyanate prepolymers of the present invention is 20 to 33% by weight, preferably 25 to 32% by weight. NCO content was determined by GB/T12009.4-2016.

The isocyanate content of the present invention is > 40wt%, preferably > 50wt%, based on the total weight of the polyurethane reaction system.

Catalyst

The polyurethane reaction system of the present invention may also include one or more catalysts. Catalysts useful in the present invention include tertiary amine-based catalysts and organotin-based catalysts. The tertiary amine catalyst includes, but is not limited to, one, two or more of triethylamine, tributylamine, dimethylethanolamine, bis (dimethylaminoethyl) ether, triethylenediamine, N-ethylmorpholine, N, N, N ', N' -tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, dimethylaminopropylenediamine, N, N, N ', N' -tetramethyldipropylenetriamine, and weak acid modified products of the amine catalyst. The content of which is from 1.0 to 5.0% by weight, preferably from 1.8 to 3.0% by weight, based on the total weight of component B.

The organotin catalyst comprises dibutyl tin dilaurate and stannous 2-ethyl hexanoate. The content of which is from 0.1 to 1.0%, preferably from 0.1 to 0.3%, based on the total weight of component B.

Foaming agent

The blowing agent used according to the invention is preferably water in an amount of from 1 to 18% by weight, preferably from 2 to 15% by weight, based on the total weight of component B.

Surface active agent

The surfactants selected according to the invention are preferably silicone oils, in an amount of from 0.1 to 2% by weight, preferably from 0.1 to 1.5% by weight, based on the total weight of component B.

Surprisingly, through repeated experimentation, we have found that the polyol compositions of the present invention comprising specific polyether polyol (e.g., B3) and B4) components and other components compatible therewith are capable of producing polyurethane foams having low densities, having specific open cells (e.g., > 50% by volume) and being more stable. The production process is simply and efficiently controlled, and foam collapse and unacceptable shrinkage are avoided, so that the yield and the production efficiency are greatly improved. And raw materials are saved, and the environment is protected.

Furthermore, we have surprisingly found that polyurethane foams produced from the polyol compositions of the present invention are capable of greatly reducing the shrinkage of the foam. In addition, the difference between the foam-spouting time and the gel time can be increased to a certain extent. Longer difference between foam-spitting time and gel time is beneficial to foam molding and stability.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that the definitions of terms herein are inconsistent with the ordinary meaning of those skilled in the art to which this invention pertains, the definitions described herein control.

Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used herein are to be understood as being modified in the art by the term "about".

As used herein, "and/or" means one or all of the elements mentioned.

The use of "including" and "comprising" herein encompasses the presence of only the recited element as well as the absence of additional non-recited elements other than the recited element.

All percentages herein are weight percentages unless otherwise indicated.

The invention will now be described by way of example only and not by way of limitation.

Examples

The model, source and proportion of each raw material are shown in the following table 1.

The test method comprises the following steps:

functionality, refers to the functionality according to the industry formula: the functionality = hydroxyl number @ molecular weight/56100; wherein the molecular weight is determined by GPC high performance liquid chromatography;

core density, which is the foam center density measured by ASTM D1622-03, measured with an overfill in the mold used in the polyurethane foam composite panel manufacturing process, i.e., the molded foam core density;

gel time refers to the time from when the reaction system A and B components begin to mix at 25℃until the viscosity reaches a certain value (e.g., about 10000 Pa.s). The gel time of the invention is measured by a gel tester. The specific test method is that the component A and the component B are mixed uniformly and then placed in a gel tester, and the time from the pressing of an opening button to the stop of the gel tester is recorded as the gel time. The gel tester used in the present invention is selected from Shanghai Senlan scientific instruments Co., ltd. (model GT-STHP-220from Shanghai SINO-LAB Instrument Co.Ltd.);

the foam-discharging time is the time from the beginning of mixing of the component A and the component B of the reaction system to the observation of obvious bubbles at the top of the foam through observation in the foaming process;

the absolute value of the foam shrinkage rate in 24 hours is a numerical value obtained according to the GB 8811-2008 test, and the absolute value is taken;

tensile strength and elongation at break were determined by DIN-53455-1981.

The types, sources and proportions of the raw materials of the invention are detailed in the following description and table 1.

Polyisocyanates, desmodur 0589, available from kesi polymer (china) limited;

polyol-1: functionality 3, hydroxyl number 35, glycerol as initiator, PO/EO-capped base polyether, 15% EO-capped, commercially available from Kogyo;

polyol-2: a functionality of 2, a hydroxyl number of 110, propylene glycol as initiator, a PO-terminated base polyether available from Ningwu chemistry;

polyol-3: functionality 2, hydroxyl number 560, ethylene glycol as initiator, EO-capped base polyether (PEG 200), available from Ningwu chemistry;

polyol-4: 10-20% (preferably 13-15%) of a base polyether capped with PO/EO, having a functionality of 3, a hydroxyl number of 37, glycerol as initiator, 73% EO cap, available from Korschu;

catalyst: KAOLIZER nr.25, CAS:1862-07-3, available from Kao Japan;

organotin catalyst: dabco T-9, available from Evonik;

foaming agent: water;

and (2) a surfactant: SBU 001, silicone oil, active ingredient siloxane, purchased from shinkava chemistry;

expanded graphite: particle size: 80 mesh, carbon content: 99.2, expansion ratio: 200ml/g, available from Qingdao Fengzhui graphite technologies Co.

Preparation of polyurethane foam of the invention

Examples 1-3 and comparative example 1:

the polyurethane foams of the respective examples and comparative examples were obtained by thoroughly mixing and foaming the components of component A polyisocyanate and component B in the specific parts by weight as listed in Table 1 at room temperature (temperature about 23 to 25 ℃ C.).

TABLE 1 Each of the component proportions (unit: weight percent wt based on the total weight of component B) of example 1 and comparative examples 1-3 and the test results obtained

Component (A)	OH.V.	Comparative example 1	Comparative example 2	Example 1	Comparative example 3
								bwt.	bwt.	bwt.	bwt.
Polyol-1	35	45.00	45.00	43.00	43.00
						Polyol-2	110	35.00	32.00	26.00	26.00
Polyol-3	560	5.00	5.00	5.00
						Polyol-4	37	2.00	5.00	13.00	13.00
Surface active agent	20	0.50	0.50	0.50	0.50
						T-9		0.20	0.20	0.20	0.20
Water and its preparation method	6233	11.00	11.00	11.00	11.00
						KAOLIZER Nr.25	386	1.00	1.00	1.00	1.00
Desmodur 0589	32.0％	170.00	170.00	170.00	170.00
								100.00	100.00	100.00	95.00
Reaction index		0.95	0.95	0.95	0.95

Expanded graphite		70	70	70	70
						Raw material temperature	℃	25±0.5	25±0.5	25±0.5	25±0.5
Water and its preparation method	％	11.1	11	11.2	11.2
						Ambient temperature	℃	23	24	23	24
Cream time	s	29	26	27	25
						Gel time	s	Collapse bubble	81	82	79
Time of bubbling	s		102	124	Collapse bubble
						Time to foam-gel time	s		21	42
Cell size	mm		Foam collapse in the process	0.3-0.5
						Core density	Kg/m ³			13.7
Surface hardness	LX-F			78
						Compressive Strength	Kpa			22
Tensile Strength	Kpa			56
						Elongation at break	％			37
Absolute value of 24-hour shrinkage		＞30％	＞30％	1.6％	＞30％

As can be seen from the test results of Table 1, the polyurethane foam produced by the polyurethane reaction system of the preferred polyol composition of the present invention comprising polyols B3 and B4 and other components compatible therewith not only has more excellent physical properties (low density, uniform cells, stable foam, etc.), but also avoids the occurrence of foam collapse and severe shrinkage which are liable to occur during foaming.

Although the invention has been described in detail hereinabove for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof except as may be defined by the claims.

Claims

1. A polyol composition comprising:

b1 2-4), weight average molecular weight of 4000-7000g/mol (test method cf. GBT 21863-2008), preferably 4500-5000g/mol, EO content of 12.0% by weight, preferably 13.0% by weight, particularly preferably 14.0-25.0% by weight, based on the total weight of B1), of EO-and/or PO-capped polyether polyols;

b2 A) functionality of 1.5 to 3, a weight average molecular weight of 600 to 1200g/mol (test methods see GBT 21863-2008), preferably 800 to 1100g/mol, PO-terminated polyether polyol;

b3 A functionality of 1.5 to 3, a weight average molecular weight of 100 to 400g/mol (test methods see GBT 21863-2008), preferably 150 to 250g/mol, EO-capped polyether polyol;

b4 A functionality of 2 to 4, a weight average molecular weight of 4000 to 6000g/mol (test methods see GBT 21863-2008), preferably 4000 to 5000g/mol, based on the total weight of the B4) component, EO content of not less than 50.0% by weight, preferably not less than 70.0% by weight, PO and/or EO-capped polyether polyol;

wherein the ratio of the contents of the components B3) and B4) B3) to B4) is < 1, preferably < 0.5, more preferably 0.1 to 0.45.

2. Polyol composition according to claim 1, wherein B1) is present in an amount of 20 to 60wt%, preferably 30 to 60wt%, based on the total weight of the polyol composition.

3. Polyol composition according to claim 1 or 2, characterized in that the content of B2) is 10-50wt%, preferably 15-40wt%, based on the total weight of the polyol composition.

4. A polyol composition according to claims 1-3, characterized in that the content of B3) is 1-15wt%, preferably 1-10wt%, based on the total weight of the polyol composition.

5. The polyol composition according to claims 1-4, wherein B4) is present in an amount of 5-25wt%, preferably 10-20wt%, more preferably 13-15wt%, based on the total weight of the polyol composition.

6. The polyol composition according to claims 1-5, characterized in that the absolute 24 hour shrinkage of the polyol composition comprising B3) to B4) < 1 is reduced by not less than 5%, preferably not less than 10% compared to a polyol composition not comprising B3) to B4) < 1 (test method GB 8811-2008).

7. Polyol composition according to claims 1-6, characterized in that the difference between the foam break-up time and the gel time of the polyurethane reaction system comprising the polyol composition is > 20 seconds, preferably > 25 seconds, more preferably 25-50 seconds.

8. The polyol composition of claims 1-7, wherein the difference in foam time and gel time of the polyurethane reaction system comprising the polyol composition of B3) to B4) < 1 increases by greater than or equal to 10%, preferably greater than or equal to 15%, as compared to a polyurethane reaction system not comprising the polyol composition of B3) to B4) to < 1.

9. A polyurethane reaction system comprising:

component A, polyisocyanate;

component B, comprising: the polyol composition of any of claims 1-8.

10. The reaction system according to claim 9, wherein the mass ratio of component a to component B is 150-180:100, preferably 165-175:100.

11. The reaction system of claim 9 or 10, wherein the polyurethane reaction system has a foam break-out time minus gel time difference of > 20 seconds, preferably ≡25 seconds, more preferably 25-50 seconds.

12. The reaction system of any one of claims 9 to 11, wherein the difference between the foam break-up time and the gel time of the polyurethane reaction system comprising B3) to B4) < 1 increases by not less than 10%, preferably not less than 15%, compared to a polyurethane reaction system not comprising said B3) to B4) to < 1.

13. A polyurethane foam produced by reacting the polyurethane reaction system of any one of claims 9-12.

14. Polyurethane foam according to claim 13, characterized in that the absolute value of the 24-hour shrinkage of the polyurethane foam is 10% or less, preferably 2% or less (test method GB 8811-2008).

15. The polyurethane foam according to claim 13 or 14, wherein the polyurethane foam produced from the polyol composition comprising B3) to B4) < 1 has an absolute reduction in 24-hour shrinkage of 5% or more, preferably 10% or more, compared to a polyurethane foam produced from a polyol composition not comprising B3) to B4) < 1 (test method GB 8811-2008).

16. A process for preparing a polyurethane foam by reacting the polyurethane reaction system of any one of claims 9-12.

17. A polyurethane product comprising the polyurethane foam of any one of claims 13-15, selected from the group consisting of automotive interiors, preferably automotive engine compartment insulation mats.