CN1159455A - Method for preparing flexible polyurethane foams - Google Patents
Method for preparing flexible polyurethane foams Download PDFInfo
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- CN1159455A CN1159455A CN96121325A CN96121325A CN1159455A CN 1159455 A CN1159455 A CN 1159455A CN 96121325 A CN96121325 A CN 96121325A CN 96121325 A CN96121325 A CN 96121325A CN 1159455 A CN1159455 A CN 1159455A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a preparation process for flexible urethane foam, comprising reacting polyatomic alcohol, organic diisocyanate and water in the presence of at least a urethane catalyzer, a siloxane-oxyalkylene copolymer and optionally another foaming agent, the surfactant thereof has the formula MDxD'yM, wherein M represents (CH3)3SiO1/2 or R(CH3)2SiO1/2, D represents (CH3)2SiO2/2, D' represents (CH3)RSiO2/2, and the value of x+y is from 48 and 220, and the ratio x/y is from 5 to 15 inclusive. In the above formulae for M and D', R is a polyether-containing substituent selected from the group consisting of (1)-CnH2nO(C2H4O)a(C3H6O)bR' moieties having weight average molecular weights of from about 2300-3200 and wherein n is 3-4, the ratio a/b is from 0.5 to 1.3 inclusive, R' represents hydrogen, an alkyl group of 1-4 carbon atoms or -C(O)CH3 and (2)-Cn'H2n'O(C2H4O)a'(C3H6O)b'R' moieties having weight average molecular weights of from about 1150-1400 and wherein n' is 3-4, a' is a number such that the ethylene oxide residues constitute 30-100% by weight of the alkylene oxide residues of the polyether, b' is a number such that the propylene oxide residues constitute 0-70% by weight of the alkylene oxide residues of the polyether, R' represents hydrogen, an alkyl group of 1-4 carbon atoms or -C(O)CH3, and the blend average molecular weight of the overall polyether-containing substituents R in the compositions is from about 1500 to 2200 and the overall EO/PO molar ratio is from about 0.65 to 1.2.
Description
The present invention relates to flexible polyurethane foam and more particularly, relate to the preparation method of the flexible polyurethane foam that contains silicone polyether surfactants, this tensio-active agent is to have siloxane backbone and oxyalkylene side group.
In the manufacturing processed of urethane foam, need tensio-active agent to come the stable foam body, until till forming the chemical reaction of polymkeric substance and fully finishing, thus foams be self-supporting and undesirable collapse can not take place.
Be used to make the material that the silicone polyether surfactants of urethane foam has siloxane backbone and pendant polyether group typically.They have two types: non-water-disintegrable and hydrolyzable.Pendant polyether group it is believed that the efficient that general acquisition is high through the non-water-disintegrable tensio-active agent that the Si-C key is connected in siloxane backbone, but has poor processing latitude.Pendant polyether group it is believed that generally have low efficient and but have wide processing latitude through the hydrolyzable tensio-active agent that the Si-OC key is connected in siloxane backbone.
The invention provides non-water-disintegrable silicone surfactant, it especially provides excellent emulsifying effectiveness, high efficient and wide processing latitude in the prescription of the foam blocks that contains high water-content and low isocyanate index in the preparation of flexible polyurethane foam piece material.And the flexible polyurethane foam piece material of producing with silicone surfactant of the present invention and is compared with the foam of other tensio-active agent production, demonstrates better foam height, and the thinner foam structure of maintenance simultaneously.
This tensio-active agent is the composition with material of following average formula:
MDxD ' yM wherein M represents (CH
3)
3SiO
1/2Or R (CH
3)
2SiO
1/2, D represents (CH
3)
2SiO
2/2, D ' expression (CH
3) RSiO
2/2, the value of x+y is that 48-220 and x/y ratio are 5 to 15.In the formula of above M and D ', R is the substituting group that contains polyethers, and this substituting group is selected from following group:
(1)-C
nH
2nO (C
2H
4O)
a(C
3H
6O)
bR ' part, its weight-average molecular weight in the 2300-3400 scope and wherein n are 3-4, and the a/b ratio is 0.5 to 1.3, R ' expression hydrogen, C
1-C
4Alkyl or-C (O) CH
3And (2)-C
N 'H
2n 'O (C
2H
4O)
A '(C
3H
6O)
B 'R ' part, its weight-average molecular weight in the 750-1400 scope and wherein n ' is 3-4, and a ' makes ethylene oxide residue account for the numeral of 30-100wt% of the alkylene oxide residue of polyethers, and b ' makes propylene oxide residue account for the numeral of 0-70wt% of the alkylene oxide residue of polyethers, and R ' expression hydrogen, C
1-C
4Alkyl or-C (O) CH
3
In addition, tensio-active agent of the present invention is formed MDxD ' yM and is contained: the substituent R that contain polyethers and weight-average molecular weight the substituent R that contain polyethers 750-1400 scope in of weight-average molecular weight in the 2300-3400 scope, with the blend molecular-weight average of the substituent R that contains polyethers whole in tensio-active agent MDxD ' yM be in the 1500-2200 scope, with oxyethane (EO) residue in two polyethers overall ratio with propylene oxide (PO) residue in two polyethers, being total EO/PO mol ratio, is in the 0.65-1.2 scope.
So, the present invention relates to the catalyzer that is used to produce urethane foam at least a, react the method for preparing flexible polyurethane foam by polyvalent alcohol, organic diisocyanate and water under the existence of dispensable another kind of whipping agent and siloxanes defined above-oxyalkylene copolymers tensio-active agent.The invention still further relates to urethane foam with this method preparation.
The tensio-active agent of Shi Yonging is the composition with material of following average formula in the present invention:
MDxD ' yM wherein M represents (CH
3)
3SiO
1/2Or R (CH
3)
2SiO
1/2, D represents (CH
3)
2SiO
2/2, D ' expression (CH
3) RSiO
2/2, the value of x+y is that 48-220 and x/y ratio are 5-15 (comprising end value).In the formula of above M and D ', R is the substituting group that contains polyethers, and this substituting group is selected from following group:
(1)-C
nH
2nO (C
2H
4O)
a(C
3H
6O)
bR ' part, its weight-average molecular weight in the 2300-3400 scope and wherein n are 3-4, and the a/b ratio is 0.5 to 1.3, R ' expression hydrogen, C
1-C
4Alkyl or-C (O) CH
3And (2)-C
N 'H
2n 'O (C
2H
4O)
A '(C
3H
6O)
B 'R ' part, its weight-average molecular weight in the 750-1400 scope and wherein n ' is 3-4, and a ' makes ethylene oxide residue account for the numeral of 30-100wt% of the alkylene oxide residue of polyethers, and b ' makes propylene oxide residue account for the numeral of 0-70wt% of the alkylene oxide residue of polyethers, and R ' expression hydrogen, C
1-C
4Alkyl or-C (O) CH
3In addition, tensio-active agent of the present invention is formed MDxD ' yM and is contained: the substituent R that contain polyethers and weight-average molecular weight the substituent R that contain polyethers 750-1400 scope in of weight-average molecular weight in the 2300-3400 scope, with the blend molecular-weight average of the substituent R that contains polyethers whole in tensio-active agent MDxD ' yM be in the 1500-2200 scope, with oxyethane (EO) residue in two polyethers overall ratio with propylene oxide (PO) residue in two polyethers, being total EO/PO mol ratio, is in the 0.65-1.2 scope.
In large-scale surfactant composition defined above of the present invention, many preferred materials are arranged.Preferred material has general average formula MD
44-63D '
5.5-12.5M.Most preferred material has average formula MD in this class
60-62D '
7-8M.The substituent R that contain polyethers of weight-average molecular weight in the 2300-3400 scope preferably the a/b ratio be 1.0 and weight-average molecular weight be approximately 3100-C
3H
6O (C
2H
4O)
a(C
3H
6O)
bR ' part.R ' preferably-C (O) CH
3
The substituent R that contain polyethers of weight-average molecular weight in the 750-1400 scope preferably contain about 43wt% ethylene oxide residue and weight-average molecular weight be about 1250-C
3H
6O (C
2H
4O)
a(C
3H
6O)
bR ' part.R ' preferably-C (O) CH
3
Tensio-active agent is formed the blend weight-average molecular weight of the substituent R that contains polyethers among MDxD ' yM preferably in the 1650-1900 scope.Overall average EO/PO mol ratio preferably about 1.0.
It is well-known being used for synthetic schedule of operation with non-water-disintegrable tensio-active agent of polyoxyalkylene side group.Representational publication sees US4, and 147,847 and 4,855,379, it is for reference that they are introduced into this paper.
Typically, tensio-active agent of the present invention is to have the average formula M of generalized by allowing
*DxD " yM
*The blend of poly-hydride siloxane and the allyl oxidation alkene polyethers of suitably selecting react in the presence of at hydrosilylation catalysts and prepare as Platinic chloride.In the formula of poly-hydride siloxane, M
*Be (CH
3)
3SiO
1/2Or (H) (CH
3)
2SiO
1/2, D is as defined above, and D " is (CH
3) (H) SiO
2/2Allyl oxidation alkene polyethers is to have end-vinyl and contain from oxyethane, propylene oxide or both to derive and the polyethers of the multiple units of coming.Reagent generally is blended in solvent such as toluene or the Virahol (2-propyl alcohol), be warming up to about 70-85 ℃, add catalyzer then, observe temperature and raise about 10-15 ℃, and final sampling and analyze the SiH group by adding the hydrogen that pure and mild alkali and measurement evaporated from mixture.If the use volatile solvent can be removed it by vacuum.
Has average formula M
*DxD " yM
*Poly-hydride siloxane prepare according to method well known in the prior art.For M
*Be (CH
3)
3SiO
1/2Situation, alkyl sily oxide such as hexamethyldisiloxane, poly-hydride siloxane polymkeric substance and alkyl annular siloxane such as octamethylcyclotetrasiloxane react in the presence of strong acid such as sulfuric acid.For M
*Be (H) (CH
3)
2SiO
1/2Situation, hydrogenation alkyl sily oxide such as dihydro tetramethyl disiloxane, poly-hydride siloxane polymkeric substance and alkyl annular siloxane such as octamethylcyclotetrasiloxane react in the presence of strong acid such as sulfuric acid.
Allyl oxidation alkene polyethers is also referred to as polyethers, equally by method preparation well known in the prior art.Allyl alcohol has substituting group not essentially on 1-or 2-position, react the required polyethers that obtains having terminal hydroxy group with oxyethane, propylene oxide or both in the presence of alkaline catalysts.It is by further reacting with alkylating agent or acylating agent such as methyl halide or diacetyl oxide, obtains alkoxyl group or ethanoyl end group respectively and by end-blocking.Certainly use other END CAPPED GROUP, comprise hydrogen, alkoxyl group or alkyl or aryl.
Making use tensio-active agent of the present invention in the flexible polyurethane foam according to method well known in the prior art.When using tensio-active agent of the present invention to produce urethane foam, one or more polyalcohols, preferred polyalkylene ethoxylated polyhydric alcohol is used for obtaining urethane bond with the polyisocyanates reaction.Average each molecule of this class polyvalent alcohol has 2.1-3.5 hydroxyl.The suitable polyvalent alcohol illustrative example that is used as a component of urethane composition is polyalkylene ether and polyester polyol.Preferred polyalkylene ethoxylated polyhydric alcohol comprises that poly-(alkylene oxide) polymkeric substance derives and polyethylene oxide and the poly(propylene oxide) polymkeric substance and the multipolymer of the terminal hydroxy group that comes as having from polyol, comprises dibasic alcohol and trivalent alcohol; Ethylene glycol is for example arranged, propylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, dimethyltrimethylene glycol, glycol ether, dipropylene glycol, tetramethylolmethane, glycerine, diglycerol, TriMethylolPropane(TMP) and similar low molecular weight polyols in the middle of them.
When enforcement is of the present invention, can use independent a kind of high molecular weight polyether.The mixture that also can use high molecular weight polyether is as two and the mixture of the material formed of trifunctional material and/or different molecular weight or different chemical.
Useful polyether glycol comprises by di-carboxylic acid and excessive diol reaction, for example hexanodioic acid and ethylene glycol or butyleneglycol reaction, or react those that are produced by lactone and excessive dibasic alcohol such as caprolactone and propylene glycol.
Except polyethers and polyester polyol, masterbatch or premix component usually contain polymer polyatomic alcohol.Polymer polyatomic alcohol is used for urethane foam and improves the anti-deformation ability of foams, promptly improves the portative power of bearing of foams.At present, two kinds of dissimilar polymer polyatomic alcohols are used for making and bear portative power and be improved.First type, be described as graft polyol, be that the trivalent alcohol of graft copolymerization is formed by therein ethylene base monomer.Vinylbenzene and vinyl cyanide are the normal monomers of selecting.Second type, the polyurea modified polyvalent alcohol is to contain the polyvalent alcohol that is reacted formed polyurea dispersions by diamine and TDI.Because the excessive use of TDI, some TDI react with polyvalent alcohol and polyureas simultaneously.This polymer polyatomic alcohol of second type has the version that is known as PIPA polyvalent alcohol (it be carry out polyreaction on the spot by TDI and alkanolamine in polyvalent alcohol formed).Depend on the needs that bear portative power, polymer polyatomic alcohol can account for the 20-80% of the polyol moiety of masterbatch.
Well-known any suitable organic multiple isocyanate prepares polyurethane products in the use prior art, this polyisocyanates for example comprises hexamethylene diisocyanate, phenylene vulcabond, tolylene diisocyanate (" TDI ") and 4,4 '-diphenylmethanediisocyanate (" MDI ").Especially suitable is 2,4-and 2, and 6-TDI is separately or together as the obtainable mixture of commercial sources.Other suitable isocyanic ester is industrially to be called " thick MDI ", is also referred to as the mixture of the vulcabond of PAPI, it contain have an appointment 60% 4,4 '-diphenylmethanediisocyanate and other isomerized and similarly more senior polyisocyanates.Also suitable is comprises " prepolymer " of these polyisocyanates of mixture of the part pre-reaction of polyisocyanates and polyethers or polyester polyol.
The suitable urea alkane catalyzer that can be used among the present invention is the known all that catalyzer of those skilled persons in the prior art, comprises tertiary amines, as triethylenediamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, tributylamine, trolamine, dimethylethanolamine and two dimethyl amido Anaesthetie Ether, and organic tin, as the sad tin that drives, stannous acetate, stannous oleate, lauric acid inferior tin, dibutyl tin laurate and other pink salt class.
Other typical reagent that can find in the flexible polyurethane foam prescription comprises chainextender such as ethylene glycol and butyleneglycol; Linking agent such as diethanolamine, diisopropanolamine (DIPA), trolamine and tripropanol amine; Especially whipping agent class, as water, liquid carbon dioxide, acetone, pentane, trichloroethane, methylene dichloride, Trichloromonofluoromethane, and analogue.
Certainly can also use other additive of giving the foams specified property.Example is the material such as fire retardant, tinting material, filler and hardness properties-correcting agent.
Urethane foam of the present invention can prepare according to any processing technology well known in the prior art, as, especially, " single stage method " foaming technique.According to this method, obtain foaming product by the reaction of carrying out polyisocyanates and polyvalent alcohol simultaneously with foaming operation.Sometimes can easily tensio-active agent be joined in the reaction mixture as the pre-composition with one or more whipping agents, polyvalent alcohol, water and catalyst component formation.
Should be appreciated that the relative consumption of the various components of foaming formulation is not undue strict.Polyvalent alcohol and polyisocyanates are present in the prescription used of preparation foams with main amount.The relative consumption of these two kinds of components in mixture is well known in the prior art.Whipping agent, catalyzer and tensio-active agent are to be enough to make a small amount of use of reaction mixture foaming.Catalyzer exists with catalytic amount, that is, this is reflected at and produces urea alkane and the needed amount of urea under the rational speed for catalysis, and tensio-active agent exists with the amount that is enough to give desired properties and stablize the foams that reacting, for example 0.4-2pphpp.
In a typical preparation method, polyvalent alcohol, water, tensio-active agent, amine catalyst and the blending together of dispensable whipping agent under agitation add tin catalyst then and final tolylene diisocyanate is sneaked into, and allow composition foam and polymerization.
Flexible polyurethane foam produced according to the invention can be used in the field identical with the conventional polyurethanes foams.For example, foams of the present invention can be used to make textile interlinings, cushioning material, mattress, packing material, carpet lining, wrapping material, packing ring, sealing member, thermal insulation material and analogous material ideally.
The general polyurethane flexible piece strand foam body prescription that contains silicone surfactant of the present invention comprises following component (parts by weight):
Flexible block strand foam body prescription
Polyvalent alcohol 100
Silicon cyanogen alkane tensio-active agent 0.4-2
Water 2-7
Auxiliary blowing agent 0-20
Amine urea alkane catalyzer 0.05-0.3
Tin urea alkane catalyzer 0.1-0.35
Isocyanate index (preferred TDI) 85-120
In a preferred flexible block strand foam body prescription, the content of water is that 6-7pphpp and isocyanic ester are indexes about 80 to the TDI that is less than in 100 the scope.
In the following embodiments, make foams according to following prescription and schedule of operation:
Voranol 3137 polyvalent alcohol 100.00pphpp
Water 6.50pphpp
DABCO CS90 amine 0.10pphpp
DABCOT-10 tin 0.32pphpp
Silicone surfactant 0.60pphpp
TDI (95 index) 67.66pphpp
The umber of the per 100 parts of polyvalent alcohols of pphpp=
1), makes and be of a size of 14 * 14 * 14 inches (ripple boxes of 35.6 * 35.6 * 35.6cm) for each foams.In addition, preparation polyethylene liner and inserting in 3.5 gallons of (13.3 liters) buckets.
2) for each serial foams, the preparation pre-composition.Pre-composition contains Voranol 3137 polyvalent alcohols (available from Dow Chemical Company), and water and DABCO CS90 amine catalyst are (available from Air Productsand Chemicals, Inc.).
3) pre-composition is weighed join in 48 ounces of (1.42 liters) dixie cups and add silicone surfactant.
4) in an independent 250ml plastic beaker, take by weighing TDI (tolylene diisocyanate).
5) DABCO T-10 catalyzer (available from Air Products and Chemicals, Inc.) is joined in the pre-composition cup and mixed 10 seconds under 2000rpm with the electronics mixing tank.The DABCOT-10 catalyzer is 50% solution of stannous octoate.
6) with in the content impouring pre-composition cup of TDI beaker and the sub-mixing tank of electricity consumption immediately under 2000rpm, mixed 7 seconds.
7) when beginning to mix the content of (containing pre-composition and TDI) cup, the electronics mixing tank starts stopwatch.
8), the bottom of the as close as possible container of lip of cup is spilt avoiding with in mixture impouring one container.
9) surplus materials in the cup is weighed.
10) for each foams, the data below obtaining: the whole rise time after 16 hours, all lifting height all solidifies height.
11) after 16 hours, foams are cut into slices.Take off from the bottom of foams and top and to be of a size of 2 * 2 * 1 inch (5.08 * 5.08 * 2.54cm) sample is used for air flow and density measurement.Basal cross section is to get from the bottom 1.5 inches (3.81cm) of foams.The top section is to get from the bottom 7.5 inches (19.05cm) of foams.
Embodiment 1
Tensio-active agent below using is made urethane foam according to the aforesaid operations program.These foams are to use box to make.
Surfactant A and B are from Osi Specialties, the commodity silicone surfactant that Inc. buys.Using them is in order to contrast.
Tensio-active agent C and D are the commodity silicone surfactants of buying from Th Goldschmidt AG..Using them is in order to contrast.
Tensio-active agent E is from Air Products and Chemical, the commodity silicone surfactant that Inc. buys.Using them is in order to contrast.
Tensio-active agent F is a silicone surfactant of the present invention, and its siloxane backbone has x+y=68 and target x/y ratio is 8.Two kinds have-C (O) CH
3The substituting group that end group contains polyethers is a side group.First kind, exist with the 35wt% of total amount, having about 3100 molecular weight and a/b ratio is 1.0.Second kind, exist with the 65wt% of total amount, having about 1250 molecular weight and a '/b ' ratio is 1.0.
Use the performance of the prepared foams of each above-mentioned tensio-active agent to be listed in table 1.In table 1, term has following meaning:
" all lifting heights " is the maximum height by millimeter that obtains in the foam uphill process.
" all solidifying height " is at room temperature to solidify the foamy maximum height of calculating by millimeter afterwards in 16-24 hour.
" %Sighback "=100 * (all lifting height-whole height that solidify)/all lifting heights
" top air flow "=under the back pressure of 0.5 inch (12.7mm) water (air flow of 5.08 * 5.08 * 2.54cm) foam samples (it is that top cross-section from foams cuts) (is pressed ft by being of a size of 2 * 2 * 1 inch
3/ min).
" bottom air flow "=under the back pressure of 0.5 inch (12.7mm) water (air flow of 5.08 * 5.08 * 2.54cm) foam samples (it is that bottom section from foams cuts) (is pressed ft by being of a size of 2 * 2 * 1 inch
3/ min).
The average bubble number of perforations of the foam sample of " abscess number "=every linear inch (2.54cm).
Table 1
| Tensio-active agent | Whole lifting heights | All solidify height | ?????％ ??Sighback | The top air flow | The bottom air flow | The abscess number |
| ????A | ????276.7 | ????268.2 | ????3.07 | ????1.6 | ????1.6 | ????9 |
| ????B | ????271.9 | ????264.2 | ????2.83 | ????8.4 | ????4.3 | ????25 |
| ????C | ????260.7 | ????251.0 | ????3.72 | ????7.5 | ????3.4 | ????25 |
| ????D | ????287.9 | ????280.2 | ????2.67 | ????3.6 | ????2.1 | ????16 |
| ????E | ????271.6 | ????262.7 | ????3.28 | ????2.1 | ????2.0 | ????6 |
| ????F | ????287.3 | ????278.2 | ????3.17 | ????7.1 | ????4.3 | ????26 |
Table 1 shows surfactant A, and D and E obtain the foams of low air flow and big abscess.Surfactant B and C obtain good aeration amount and foam structure, but obtain low abscess height.Have only tensio-active agent F of the present invention to obtain having thin foam structure, the foams of high air flow and high height (all of high-quality flexible foam must characteristic).
Embodiment 2
The tensio-active agent of listing in the use table 2 is made urethane foam (these foams prepare) according to the aforesaid operations program in bucket.Tensio-active agent is the compound with formula MDxD ' yM, and wherein M represents (CH
3)
3SiO
1/2, D represents (CH
3)
2SiO
2/2, D ' expression (CH
3) RSiO
2/2, R is the substituting group that contains polyethers, this substituting group is selected from: (1) weight-average molecular weight be about 3100-C
3H
6O (C
2H
4O)
a(C
3H
6O)
bC (O) CH
3(2) weight-average molecular weight be about 1250-C
3H
6O (C
2H
4O)
A '(C
3H
6O)
B 'C (O) CH
3X, y, a, b, a ', b ', the blend average mark that contains the substituent R of polyethers in tensio-active agent all is listed in the table below 2 in amount with for the value of total EO/PO molar ratio of each tensio-active agent.
Table 2
| Tensio-active agent | ???x | ???y | ??a | ??b | ??a′ | ??b′ | Average polyethers Mw | Total EO/PO mol ratio |
| ????F | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1664 | ????1 |
| ????G | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1500 | ????1 |
| ????H | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1727 | ????1 |
| ????I | ??56.7 | ??11.3 | ??30 | ??30 | ??12 | ??12 | ??1500 | ????1 |
| ????J | ??56.7 | ??11.3 | ??30 | ??30 | ??12 | ??12 | ??1727 | ????1 |
| ????K | ??42.7 | ??5.3 | ??30 | ??30 | ??12 | ??12 | ??1500 | ????1 |
| ????L | ??42.7 | ??5.3 | ??30 | ??30 | ??12 | ??12 | ??1727 | ????1 |
| ????M | ??40.0 | ??8.0 | ??30 | ??30 | ??12 | ??12 | ??1500 | ????1 |
| ????N | ??40.0 | ??8.0 | ??30 | ??30 | ??12 | ??12 | ??1727 | ????1 |
| ????O | ??51.6 | ??6.4 | ??30 | ??30 | ??12 | ??12 | ??1664 | ????1 |
| ????P | ??51.6 | ??6.4 | ??30 | ??30 | ??12 | ??12 | ??1795 | ????1 |
| ????Q | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1795 | ????1 |
| ????R | ??56.0 | ??7.0 | ??30 | ??30 | ??12 | ??12 | ??1727 | ????1 |
| ????S | ??54.6 | ??8.4 | ??30 | ??30 | ??12 | ??12 | ??1605 | ????1 |
| ????T | ??54.0 | ??9.0 | ??30 | ??30 | ??12 | ??12 | ??1605 | ????1 |
| ????U | ??54.0 | ??9.0 | ??25 | ??25 | ??12 | ??12 | ??1560 | ????1 |
| ????V | ??54.0 | ??9.0 | ??30 | ??30 | ??15 | ??15 | ??1909 | ????1 |
| ????W | ??54.0 | ??9.0 | ??30 | ??30 | ??18 | ??18 | ??2193 | ????1 |
| ????X | ??169.0 | ?23.0 | ??18 | ??18 | ??12 | ??0 | ??1477 | ??1.4 |
The foams that the use of tensio-active agent F-W in foaming formulation causes all these tensio-active agents to obtain.Have total EO/PO molar ratio and be 1.4 tensio-active agent X, obtained to have the foams of thick abscess and low air flow.
Embodiment 3
The tensio-active agent of listing in the use table 3 is made urethane foam according to the aforesaid operations program.This tensio-active agent have with embodiment 2 in the identical formula of employed those tensio-active agents.X, y, a, b, a ', b ', in tensio-active agent, contain polyethers substituent R the blend molecular-weight average and all be listed in the table below 3 for the value of total EO/PO molar ratio of each tensio-active agent.
Table 3
| Tensio-active agent | ???x | ???y | ??a | ??b | ??a′ | ??b′ | Average polyethers Mw | Total EO/PO mol ratio |
| ????Y | ??60.4 | ??7.6 | ??30 | ??30 | ??8 | ??15 | ??1866 | ??0.74 |
| ????Z | ??60.4 | ??7.6 | ??30 | ??30 | ??8 | ??15 | ??1662 | ??0.68 |
| ????A′ | ??60.4 | ??7.6 | ??30 | ??30 | ??8 | ??15 | ??1498 | ??0.61 |
| ????B′ | ??60.4 | ??7.6 | ??30 | ??30 | ??10 | ??4 | ??1242 | ??1.53 |
| ????C′ | ??60.4 | ??7.6 | ??30 | ??30 | ??10 | ??4 | ??910 | ??2.03 |
| ????D′ | ??60.4 | ??7.6 | ??30 | ??30 | ??10 | ??4 | ??1050 | ??1.76 |
| ????E′ | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1333 | ??1.00 |
| ????F′ | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1434 | ??1.00 |
| ????G′ | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1640 | ??1.00 |
| ????H′ | ??60.4 | ??7.6 | ??30 | ??30 | ??12 | ??12 | ??1916 | ??1.00 |
Measure whole lifting heights of foams then according to the aforesaid operations program, all solidify height, %Sighback, top air flow and bottom air flow.Measurement result is recorded in the following table 4.
Table 4
| Tensio-active agent | Whole lifting heights | All solidify height | ?????％ ??Sighback | The top air flow | The bottom air flow |
| ??Y | ??351.10 | ??324.43 | ????7.60 | ??7.56 | ??6.17 |
| ??Z | ??327.46 | ??268.28 | ????18.07 | ??6.21 | ??5.54 |
| ??A′ | Poreization, all collapse | ||||
| ??B′ | ??336.15 | ??282.84 | ????15.86 | ??2.64 | ??3.14 |
| ??C′ | Gross porosityization, all collapse | ||||
| ??D′ | Gross porosityization, all collapse | ||||
| ??E′ | ??313.80 | ??90.00 | ????71.32 | ??- | ??- |
| ??F′ | ??337.03 | ??228.56 | ????32.19 | ??5.15 | ??4.49 |
| ??G′ | ??342.68 | ??320.28 | ????6.54 | ??6.63 | ??5.40 |
| ??H′ | ??346.23 | ??322.57 | ????6.83 | ??7.07 | ??6.30 |
The use of tensio-active agent of the present invention in foaming formulation obtained high-quality foams, with surfactant A '-F ' compares, the latter's foams or collapse or have poor foam characteristic.
Claims (12)
1, the method for preparing flexible polyurethane piece strand foam body, be included at least a urea alkane catalyzer, under existing, siloxanes-oxyalkylene copolymers tensio-active agent and dispensable another kind of whipping agent allow polyvalent alcohol, organic diisocyanate and water react, and it is characterized in that this siloxanes-oxyalkylene copolymers tensio-active agent has following average formula:
MDxD ' yM wherein M represents (CH
3)
3SiO
1/2Or R (CH
3)
2SiO
1/2, D represents (CH
3)
2SiO
2/2, D ' expression (CH
3) RSiO
2/2, the value of x+y is that 48-220 and x/y ratio are 5 to 15.In the formula of above M and D ', R is the substituting group that contains polyethers, and this substituting group is selected from following group:
(1)-C
nH
2nO (C
2H
4O)
a(C
3H
6O)
bR ' part, its weight-average molecular weight in the 2300-3400 scope and wherein n are 3-4, and ratio a/b is 0.5 to 1.3, R ' expression hydrogen, C
1-C
4Alkyl or-C (O) CH
3With
(2)-C
N 'H
2n 'O (C
2H
4O)
A '(C
3H
6O)
B 'R ' part, its weight-average molecular weight in the 750-1400 scope and wherein n ' is 3-4, and a ' makes ethylene oxide residue account for the numeral of 30-100wt% of the alkylene oxide residue of polyethers, and b ' makes propylene oxide residue account for the numeral of 0-70wt% of the alkylene oxide residue of polyethers, R ' expression hydrogen, C
1-C
4Alkyl or-C (O) CH
3, the blend molecular-weight average of whole substituent R that contains polyethers is in the 1500-2200 scope and total EO/PO mol ratio is in the 0.65-1.2 scope in the tensio-active agent.
2, according to the method for claim 1, wherein the value of x+y is about 68, the x/y ratio be about 8 and R comprise that the weight-average molecular weight of having of 35wt% about 3100 and a/b ratio are that have about 1250 weight-average molecular weight and a '/b ' ratio of 1.0 first kind substituting group that contains polyethers and 65wt% is second kind of substituting group that contains polyethers of 1.0.
3, according to the process of claim 1 wherein the value of x in the 44-63 scope and the value of y in the 5.5-12.5 scope.
4, basis the process of claim 1 wherein that the value of x is in the 60-62 scope and the value of y is in the 7-8 scope.
5, according to the process of claim 1 wherein that R ' is-C (O) CH
3
6, according to the method for claim 2, wherein R ' is-C (O) CH
3
7, according to the method for claim 3, wherein R ' is-C (O) CH
3
8, according to the method for claim 4, wherein R ' is-C (O) CH
3
9, according to the process of claim 1 wherein that (2) contain about 43wt% ethylene oxide residue and weight-average molecular weight is about 1250-C
3H
6O (C
2H
4O)
a(C
3H
6O)
bR ' part.
10, according to the method for claim 9, wherein R ' is-C (O) CH
3
11, according to the process of claim 1 wherein that the blend weight-average molecular weight that contains the substituent R of polyethers in the tensio-active agent is 1650 to 1900.
12, according to the process of claim 1 wherein that total EO/PO molar ratio is 1.0.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57758895A | 1995-12-22 | 1995-12-22 | |
| US577,588 | 1995-12-22 | ||
| US577588 | 1996-12-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1159455A true CN1159455A (en) | 1997-09-17 |
| CN1069326C CN1069326C (en) | 2001-08-08 |
Family
ID=24309377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96121325A Expired - Fee Related CN1069326C (en) | 1995-12-22 | 1996-12-21 | Method for preparing flexible polyurethane foams |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1069326C (en) |
| BR (1) | BR9606155A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015838B (en) * | 2008-04-03 | 2014-03-12 | 迈图高新材料责任有限公司 | Polyurethane foams containing silicone surfactants |
| CN109134809A (en) * | 2018-08-07 | 2019-01-04 | 苏州思德新材料科技有限公司 | A kind of pore type polyurethane foam material and preparation method thereof |
| CN109196014A (en) * | 2016-04-12 | 2019-01-11 | 赢创德固赛有限公司 | Siloxane-oxyalkylene copolymer surfactants composition |
-
1996
- 1996-12-21 CN CN96121325A patent/CN1069326C/en not_active Expired - Fee Related
- 1996-12-23 BR BR9606155A patent/BR9606155A/en active Search and Examination
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015838B (en) * | 2008-04-03 | 2014-03-12 | 迈图高新材料责任有限公司 | Polyurethane foams containing silicone surfactants |
| CN109196014A (en) * | 2016-04-12 | 2019-01-11 | 赢创德固赛有限公司 | Siloxane-oxyalkylene copolymer surfactants composition |
| US11098198B2 (en) | 2016-04-12 | 2021-08-24 | Evonik Operations Gmbh | Siloxane-oxyalkylene copolymer surfactant compositions |
| CN109134809A (en) * | 2018-08-07 | 2019-01-04 | 苏州思德新材料科技有限公司 | A kind of pore type polyurethane foam material and preparation method thereof |
| CN109134809B (en) * | 2018-08-07 | 2021-01-12 | 苏州思德新材料科技有限公司 | Fine-pore polyurethane foam material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9606155A (en) | 1998-09-01 |
| CN1069326C (en) | 2001-08-08 |
| MX9606623A (en) | 1998-06-28 |
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