CN101085825A - Method for producing high elasticity and cold curing polyurethane foam - Google Patents

Abstract

The invention relates to a method for preparing high- elasticity and cold- curing polyurethane foam. The organic polysiloxane is added into reaction raw material with its weight being 0.01- 2.0% of the raw material weight, the general formula of said organic polysiloxane is shown in formula I. The R1 is metyl group or R2, R2 is methyl chlorine, n is number from 0 to 12, when R1 is metyl group, m is number of 1- 8, and when R1 is methyl chlorine, m is number of 0- 6. The product is characterized by more coarse porous structure and higher elasticity. The openings of foam are much more if checked by contact method.

Description

Produce the method for snappiness, cold curing polyurethane foam

Invention field

The present invention relates to a kind of by dual functional at least polymeric polyisocyanate and dual functional at least polyvalent alcohol and catalyzer, water and/or whipping agent, as the method for the organic functional silicone of stablizer and optional other Additive Production snappiness, cold curing polyurethane foam.

Background technology

A kind of dual functional at least polymeric polyisocyanate is adopted in the cold foamy production of high resilience polyurethane, for example tolylene diisocyanate or diphenylmethanediisocyanate have at least two hydroxyls with each molecule and most ofly on average react for the polyvalent alcohol of primary hydroxyl.Such polyvalent alcohol adopts following method preparation usually: at first add propylene oxide in raw alcohol, in this adduct, add oxyethane then, the add-on of described oxyethane makes at least 40% hydroxyl, and preferred 70% to 90% hydroxyl exists with the form of primary hydroxyl.

Because the high-content of primary hydroxyl, these polyvalent alcohols show hyperergy to isocyanic acid.Therefore, in foaming process, can reach high crosslink density, this and conventional polyurethane foam, promptly so-called thermal foam difference.Its advantage is that slaking can take place under the situation that external energy is not provided, and has shortened the required time of slaking on the whole.Yet also there is following shortcoming in this method: the tendency that promptly forms closed-cell foam increases and the decline of admissible mismachining tolerance.Admissible mismachining tolerance is interpreted as tolerance limit, departs from the entail dangers to not of filling a prescription to forming stable and being the foam of perforate simultaneously in tolerance limit.

But the decline of the permissible error that is caused by the hyperergy of foaming component, and the formation that causes is stable and foamy scope still perforate is narrow, makes these products can't be used as suds-stabilizing agent, although stablizer successfully is used to produce so-called thermal foam.In addition, such stablizer will make foam have undesirable fine and closely woven and regular pore structure.

Because foaming raw material has hyperergy, therefore say in principle, in the production of snappiness, cold curing polyurethane foam, by using isocyanic ester or the polyethers and the low-molecular-weight multifunctional linking agent of higher functional, might under the situation of not adding suds-stabilizing agent, obtain stable foam.Yet, in this way the foam of Huo Deing have unjustified pore structure and, say further, be closed-cell foam substantially, therefore do not have operability technically.

For regulating above-mentioned foamy pore structure, can use low-molecular-weight methyl polysiloxane or phenyl methyl polysiloxane, as German Patent 2,533,074 and the uncensored open text (Offenlegungsschrift) 2,221 of German patent application, 811 is described.In this way, in a close limit, obtain to have adjusted the foam of the abundant perforate of pore structure.Yet, almost do not have admissible mismachining tolerance, and this foamy physicals is not suitable for a lot of application.Owing to have high-crosslinking-degree, the value of described foamy tension fracture and tear strength is all lower.

For overcoming above-mentioned shortcoming, developed multiple snappiness foam, its preparation raw material is except reactive polyvalent alcohol, mainly contain the bifunctional isocyanate, for example pure tolylene diisocyanate or tolylene diisocyanate and 20% or be lower than 20% the diphenylmethane diisocyanate fat and the mixture of little amount of crosslinking agent.For improving above-mentioned foamy hardness, except using the polyvalent alcohol of forming by propylene oxide and oxyethane, can use following polyvalent alcohol in addition, described polyvalent alcohol contains Chemical bond or physics dispersive polymeric component, for example vinyl cyanide and cinnamic polymkeric substance or polymerization urea derivatives.

Prescription does not based on this generate stable foam naturally, unless promptly add stablizer, the foam bubble that can collapse after initiation.Therefore the required suds-stabilizing agent of above-mentioned foam must rise and prevent the stabilization of bubble of collapsing, and regulates abscess, and guarantees to form open celled foam in wide as far as possible scope.

Developed the compound that satisfies above-mentioned requirements, and the suds-stabilizing agent of prior art can be divided into two classes.

One class is formed by polysiloxane-polyoxyalkylene copolymers, and wherein the molecular weight of polysiloxane block is 150 to 2,500, and the molecular weight of polyoxyalkylene block is 150 to 1,500.Product is hydroxyl not.This series products and the purposes in polyurethane foam thereof are described in United States Patent (USP) 3,741, in 917 and 4,031,044.

Another kind of stablizer comprises by the polysiloxane of organic group modification.Described organic group is a Qing Wanji (United States Patent (USP) 3,952,038), cyanogen alkoxyalkyl (the open text (Auslegeschrift) 2,402,690 that German patent application has been examined), tetramethylene sulfone base oxygen base alkyl (sulfolanyloxyalkyl) (United States Patent (USP) 4,110,272), 4-morpholino alkoxyalkyl (United States Patent (USP) 4,067,828) and uncle's hydroxyalkyl (United States Patent (USP) 4,039,490).

And the verified polysiloxane with chloromethyl body (entity) is very useful.The polysiloxane that described chloromethyl replaces, as the stablizer of producing snappiness, cold curing polyurethane foam, the existing description in the uncensored open text 2,736,138 of German patent application.

The present invention sets about from prior art, and employed chloromethylation polysiloxane in the method for the uncensored open text 2,736,138 of German patent application is improved.

A shortcoming of aforementioned polysiloxane is its synthetic required parent material, even if be not possible hardly, also is to be difficult to obtain with technical scale.Certainly, might synthesize simple function dimethyl chloride methyl chlorosilane by the photochemical catalysis halogenation of trimethylchlorosilane.Yet difunctionality methyl chloride dimethyl dichlorosilane (DMCS) synthetic caused suitable difficulty, and therefore, for economic reasons, the simple function silane that in fact has only chloromethyl to replace can be for the synthetic usefulness of industry.So have only α so far, the methyl polysiloxane that ω-chloromethyl replaces has commercially available.

Surprisingly, determined that the polysiloxane that corresponding chloropropyl replaces is easier to obtain, and its stability is better than the siloxanes that chloromethyl replaces.At present, also may be not only synthetic economically α, the siloxanes that ω-chloropropyl replaces, and the bifunctional in these siloxanes, promptly the siloxy units of chaining also has the chloropropyl group.What by the way, can be used in the inventive method is fit to the condition that requires according to prescription and performance more through the siloxanes of modification.

Goal of the invention

Therefore, main purpose of the present invention is to improve method of the prior art to produce snappiness, cold curing polyurethane foam.

Summary of the invention

According to the present invention, be in the presence of the organic functional silicone of general formula I of 0.01 weight-2.0 weight % (in polyvalent alcohol) at value, prepare described foam,

Wherein,

R ¹Represent methylidene or R ²,

R ²Represent chloropropyl,

N is 0-12,

Work as R ¹During for methyl, m is 1-8, and

Work as R ¹During for chloropropyl, m is 0-6.

The preferred organic functional silicone that uses with general formula I I,

Wherein,

R ²Be chloropropyl,

N ' is 1-10, and

M ' is 1-6.

The polysiloxane that is used for the inventive method can use separately or use with siloxanes well known in the prior art.

With regard to the inventive method, can use reactive component known and habitual in the high resilience polyurethane foam production and additive.

For dual functional at least polymeric polyisocyanate, can use the isomer of tolylene diisocyanate, the isomer or the oligocene methylene isocyanic ester of two isocyanato-ditans.

The per molecule polyvalent alcohol has at least 2,2 to 8 hydroxyls especially, wherein on average, and at least 40%, preferred 70-90% is primary hydroxyl.Molecular weight/hydroxyl (equivalent) is 700-3,000.Polyvalent alcohol can be made up of oxygen ethene and oxypropylene body fully.But Chemical bond or physics are dispersed with other polymerization substituting groups of 30 weight % at the most in polyvalent alcohol.Described other polymeric components have, for example, and the polymkeric substance of vinylbenzene or vinyl cyanide or its multipolymer, and for example, the organic urea derivatives of polymerization.

For catalyzer, use common catalyzer, for example the organic salt of tin and tertiary amine.

Suitable whipping agent is common known water and chlorofluorocarbon with foaming purposes.Other additive has fire retardant, for example chloroalkyl phosphate esters, and inert filler and pigment.

The organic functional silicone that is used for the inventive method can be synthesized by cohydrolysis and the condensation of common known method by simple function and difunctionality chlorosilane.Chloropropyl can obtain by suitable silane that has the SiH key and propenyl chloride are reacted in common known mode.

Compare with the foam for preparing according to the uncensored method that discloses the prior art that discloses in the text 2,736,138 of German patent application, the polyurethane foam that is made by the inventive method has roughish pore structure, so elasticity is higher.According to the foam that the present invention produces, its perforate degree that presses the foam materials that method (impression force) records is higher.The verified polysiloxane that is used for the inventive method and has horizontal (lateral) chloropropyl body, promptly the chloropropyl body is distributed in the chain, and its balance between stability and perforate is better.

In following examples, the excellent properties that organic functional silicone had that is used as stablizer in the conventional foam formulation in this area in the methods of the invention will be showed, be understood that described embodiment provides in the mode of example, and do not limit the present invention in any way.

1. moulded foam

The test foam process

The prescription 1-3 listed component except that polymeric polyisocyanate weighed and the 2L beaker of packing in, the usefulness spiral stirrer was with 500RPM stirring 60 seconds.The polymeric polyisocyanate that adds sufficient quantity then, and 2, the restir mixture is 7 seconds under the 000RPM.Reaction mixture is added in the aluminum dipping form of 40 * 40 * 10cm, described aluminum dipping form has been preheated to 45 ℃ and has also used the releasing agent pre-treatment.The module setting time of listed prescription 1-3 is 8 minutes.

The evaluation of moulded foam

For determining to press power, foam segment is removed from mould carefully.Promptly be engraved in the foam segment that did not apply any pressure as yet then and measure the penetration hardness that it compresses at 50% o'clock.The area of the circle impression that uses for this purpose is 300cm ²After the pressure release, wash (extensive fulling) by extensively contracting the closed pore that exists in the foam segment is opened.Then, measure 50% o'clock penetration hardness of compression once more.Be the tolerance of the power of pressing with the difference between two values of newton (N) expression.

In addition, also estimated the degree of uniformity of hole count/cm and pore structure.

Adopt following high resilience polyurethane moulded foam prescription that polysiloxane copolymer used according to the invention is tested.

Prescription 1 (moulded foam)

Polyvalent alcohol 1 60

Polyvalent alcohol 2 40

Water (total amount) 4.3

Diethanolamine 1.5

TEGOAMIN ^(R)33 ¹⁾ 0.5

TEGOAMIN ^(R)BDE ²⁾ 0.07

KOSMOS ^(R)21 ³⁾ 0.05

The suds-stabilizing agent variable

TDI 80/20 44.7

Marker (index) 87

Prescription 2 (moulded foams)

Polyvalent alcohol 1 75

Polyvalent alcohol 2 25

Water (total amount) 3.1

Diethanolamine 0.7

TEGOAMIN ^(R)33 ¹⁾ 0.4

TEGOAMIN ^(R)BDE ²⁾ 0.12

KOSMOS ^(R)19 ⁴⁾ 0.02

TDI 80/20 37.0

Marker 100

Prescription 3 (moulded foams)

Polyvalent alcohol 1 65

Polyvalent alcohol 3 35

Water (total amount) 3.9

TEGOAMIN ^(R)33 ¹⁾ 0.3

TEGOAMIN ^(R)BDE ²⁾ 0.08

Niax ^(R)A 107 ⁵ 0.15

KOSMOS ^(R)21 ³⁾ 0.02

Isocyanate mixture is

22% thick MDI 40.3

78% TDI 80,/20 84

Following mixture is used as suds-stabilizing agent:

A. the molecular weight that polychlorostyrene propyl group-polysiloxane of 10 weight % is dissolved in 90 weight % is in pure poly-(propylene oxide) polyethers of 400.

B. polychlorostyrene propyl group-polysiloxane of 10 weight % being dissolved in the polyethers A of 83 weight % and the chain length of 7 weight % is in the polydimethylsiloxane part of N=5-9.

Following polysiloxane is used to prepare mixture A and B:

I. the uncensored open text 2,736 of German patent application, the stablizer described in 138

II. general formula I of the present invention, wherein n=3, m=2, R ₁=CH ₃

III. general formula I of the present invention, wherein n=3, m=1, R ₁=CH ₃

Contrast stablizer I uses with pure form, i.e. not diluted.

Embodiment 1

Below for to 1 result who adopts the stabilizer blend A contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fills a prescription:

Stablizer	Weight %	Press power N	Hole/cm	Elasticity %	Pore structure	The epidermis situation
							I II III	0.2 0.25 0.35 0.5 0.3 0.5 0.75 1.0 0.3 0.5 0.75 1.0	120 125 130 145 65 60 60 63 60 58 7 63	- 10 11 12 - 7 8 8 - 8 8 9	- 52 53 49 - 57 58 60 - 55 55 58	The regular transformation rule rule of the regular transformation rule of transformation rule rule	The good distortion of gross distortion gross distortion gross distortion gross distortion distortion slight deformation is good good

Embodiment 2

Below for to 1 result who adopts the stabilizer blend B contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fills a prescription:

Stablizer	Weight %	Press power N	Hole/cm	Elasticity %	Pore structure	The epidermis situation
							I	0.2 0.25 0.35 0.5	120 125 130 145	- 10 11 12	- 52 53 49	Transformation rule rule rule	Gross distortion gross distortion gross distortion gross distortion

II III

0.3 0.5 0.75 1.0 0.3 0.5 0.75 1.0

80 70 70 65 75 74 70 65

8 9 10 10 9 9 10 10

- 53 55 56 54 53 53 54

Rule rule rule rule rule rule rule rule

The good slight deformation of distortion slight deformation is good good

Embodiment 3

Below for to 2 results that adopt the stabilizer blend A contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fill a prescription:

Stablizer	Weight %	Press power N	Hole/cm	Elasticity %	Pore structure	The epidermis situation
							I II III	0.3 0.5 0.75 1.0 0.5 1.0 1.5 2.0 0.5 1.0 1.5 2.0	140 140 155 170 110 105 102 90 120 110 105 90	- 10 12 15 - - 8 9 - 8 9 9	- 54 55 52 - - 59 58 - 57 59 61	Transformation rule rule rule distortion transformation rule rule transformation rule rule rule	Distortion distortion distortion distortion distortion distortion distortion is good

Embodiment 4

Below for to 2 results that adopt the stabilizer blend B contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fill a prescription:

Stablizer	Weight %	Press power N	Hole/cm	Elasticity %	Pore structure	The epidermis situation
							I II III	0.3 0.5 0.75 1.0 0.5 1.0 1.5 2.0 0.5 1.0 1.5 2.0	140 140 155 170 90 75 80 110 85 90 90 90	- 10 12 15 - 9 9 11 - 9 10 12	- 54 55 52 - 56 55 55 - 56 56 54	The regular transformation rule rule of the regular transformation rule of transformation rule rule	Distortion distortion distortion distortion distortion distortion distortion distortion distortion is good good

Embodiment 5

Below for to 3 results that adopt the stabilizer blend A contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fill a prescription:

Stablizer	Weight %	Press power N	Hole/cm	Elasticity %	Pore structure	The epidermis situation
							I II III	0.3 0.5 0.75 1.0 0.5 0.75 1.0 1.5 0.5 0.75 1.0 1.5	130 100 110 130 120 110 110 100 130 105 100 105	10 11 12 14 - 8 9 9 - 8 9 9	49 52 51 48 - 52 54 52 - 50 50 53	The regular transformation rule rule of regular transformation rule rule	The good distortion of the good good distortion distortion of distortion is good good

Embodiment 6

Below for to 3 results that adopt the stabilizer blend B contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fill a prescription:

Stablizer	Weight %	Press power N	Hole/cm	Elasticity %	Pore structure	The epidermis situation
							I II III	0.3 0.5 0.75 1.0 0.5 0.75 1.0 1.5 0.5 0.75 1.0 1.5	130 100 110 130 70 75 80 90 75 75 80 85	10 11 12 14 9 10 10 11 9 10 10 12	49 52 51 48 56 55 55 55 52 53 54 52	Rule rule rule rule rule rule rule rule rule rule rule rule	Distortion is good good good

2. block foam

Technology

This test adopts the low press of Admiral two components to carry out.The velocity of discharge of polyvalent alcohol is 10kg/min.Foaming process occurs in the open top container that size is 100 * 60 * 60cm.

The evaluation of block foam

For estimating the effect of different suds-stabilizing agents under different concns, for the visible foam opens and carries out qualitative evaluation by bubbling (blow off) in the block foam.Measurement presses power, foamy porosity (porosity) and presses back foamy elasticity.In addition, the hole count/cm of block foam and the uniformity coefficient of pore structure have also been estimated.Measure and carry out as follows:

Estimate and bubble

Do not bubble to having, slightly bubble and well bubble and distinguish.If foamy projection epidermis opens equably on whole width when the reaction of rising finishes, then be referred to as good foaming.

Elastic measurement

Adopt ASTM D 1564 ball rebound tests.

The measurement of porosity

The value that illustrates is the block foam required back-pressure of constant gas that represent with millimeter water column, that keep 6L/min by thick 10cm, lateral area 30 * 30cm.The perforate of the low more expression foamy of observed value is many more.

Press force measurement

For carrying out described measurement.In being the open top container of 25 * 25 * 25cm, size foams.Depress storage after 2 days at standard atmosphere, cut top (peak) at high 20cm place.On untouched and the foam of washing that fully contracts, measure penetration hardness.The difference of representing with N between the two is the required power of compressing abscess.Usable floor area is 100cm ²Square impression measure indentation force.

Press power, porosity is closely related with elastic value, and represents the metric of the perforate of foam after it is made.Because the residue of hole window (cell window) left behind after pressing, and has hindered passing through of air, even the foam of therefore initial closed pore is after pressing, its porosity and elastic value are also lower.

Further adopt following high resilience polyurethane block foam prescription that polysiloxane copolymer used according to the invention is tested:

Prescription 4 (block foams)

Polyvalent alcohol 4 100

Water (total amount) 3.2

Diethanolamine 1.3

TEGOAMIN ^(R) BDE 0.1

TEGOAMIN ^(R)33 0.2

KOSMOS ^(R)29 0.2

Suds-stabilizing agent 80 variablees

T 80 43.3

Marker 110

Embodiment 7

Below for to 4 results that adopt the stabilizer blend B contain polychlorostyrene propyl group-siloxanes II and III and contrast stablizer I to be obtained that fill a prescription:

Stablizer	Weight part	Rise time	Bubble	Press power N	Elasticity	Porosity	Hole/cm
								I II	0.2 0.6 1.2 0.2 0.6 1.2	118 114 108 125 108 106	It is light strong not have light nothing	170 150 130 140 90 80	55 57 57 56 58 59	38 32 19 28 20 11	8 10 10 8 9 9

Explanation to employed raw material description among the prescription 1-4:

Polyvalent alcohol 1:Voranol ^(R)CP 4711, and Dow Chemical, hydroxyl value are 35,18% oxyethane, 80% primary hydroxyl

Polyvalent alcohol 2:Desmophen ^(R)7617, Bayer AG, hydroxyl value are 28,20% solid (PHD)

Polyvalent alcohol 3:Niax ^(R)34-28, Union Carbide, hydroxyl value are 28,20% solid (acrylonitritrile-styrene resin)

Polyvalent alcohol 4:Niax ^(R)CM 11, and Union Carbide, hydroxyl value are 32,10% solid (acrylonitritrile-styrene resin)

TEGOAMIN ^(R)33 ¹⁾: the dipropylene glycol solution of 33% triethylenediamine, Th.Goldschmidt AG

TEGOAMIN ^(R)BDE ²⁾: the dipropylene glycol solution of two (dimethyl aminoethyl) ethers of 70%, Th.Goldschmidt AG

KOSMOS ^(R)21 ³⁾: the dibutyl tin of two thiolate types (IV), Th.Goldschmidt AG

KOSMOS ^(R)21 ⁴⁾: the dibutyl tin of dilaurate type (IV), Th.Goldschmidt AG

TEGOAMIN ^(R)33 ¹⁾: the dipropylene glycol solution of two (dimethyl aminoethyl) ether manthanoate of 70%

Embodiment 1-6 confirms to adopt polychlorostyrene propyl group-polysiloxane of the present invention, can obtain following effect:

A) stabilizer concentration be starkly lower than the contrast stabilizer concentration situation under can make foam stabilization;

B) prepared foamy perforate (pressing power) obviously is better than the prepared foamy perforate with chloromethyl modified product I;

C) character of epidermis especially in colder mould (45 ℃), is used the epidermis character of the foam pad of the polyvalent alcohol preparation that contains organic filler, significantly is better than the epidermis character of contrast product I.

Embodiment 7 confirms that except that embodiment 1-6, described polychlorostyrene propyl group-polysiloxane also can be used for stablizing the high resilience polyurethane block foam.

Claims (6)

1. method for preparing snappiness, cold curing polyurethane foam, this method is included under the existence as the organic functional silicone of stablizer, adopt dual functional at least polymeric polyisocyanate, dual functional at least polyvalent alcohol, catalyzer, water and/or whipping agent to foam, wherein said organic functional silicone has general formula

Wherein,

R ¹Be methyl or R ²,

R ²Be chloropropyl,

N is 0-12,

Work as R ¹During for methyl, m is 1-8, and

Work as R ¹During for chloropropyl, m is 0-6.

2. the process of claim 1 wherein that this foaming mixtures contains the described polysiloxane in 0.01 weight %-2.0 weight % of the polyvalent alcohol in the mixture.

3. the method for claim 2, wherein said organic functional silicone has general formula

Wherein,

R ²Be chloropropyl,

N ' is 1-10, and

M ' is 1-6.

4. in the method for claim 1, wherein this dual functional at least polymeric polyisocyanate isomer that is tolylene diisocyanate, the isomer or the oligocene methylene isocyanic ester of two isocyanato-ditans, this dual functional at least polyvalent alcohol per molecule has 2 to 8 hydroxyls simultaneously, and wherein average 70-90% is a primary hydroxyl.

5. the described method of claim 4, wherein this polyvalent alcohol is made up of oxygen ethene and oxypropylene unit.

6. the described method of claim 4, wherein this polyvalent alcohol comprises oxygen ethene and the oxypropylene unit as major portion, described unit contains vinylbenzene or the acrylonitrile polymer of 30 weight % at the most.