CA2233472A1 - Polymer polyol and preformed stabilizer systems - Google Patents
Polymer polyol and preformed stabilizer systems Download PDFInfo
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- CA2233472A1 CA2233472A1 CA002233472A CA2233472A CA2233472A1 CA 2233472 A1 CA2233472 A1 CA 2233472A1 CA 002233472 A CA002233472 A CA 002233472A CA 2233472 A CA2233472 A CA 2233472A CA 2233472 A1 CA2233472 A1 CA 2233472A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules
- C08F291/08—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules on to macromolecules containing hydroxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
A preformed stabilizer composition based on a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280 is used to manufacture polymer polyol compositions having a combination of (a) high polymer content, from 30 weight percent to 60 weight percent, (b) lower viscosities, typically less than 9,000 centipoise, (c) product stability such that 100 % passes through a 150 mesh screen, and (d) up to 100 % of the polymer solids content passes through a 700 mesh screen.
Description
W O 97/15605 PCT~EP95/04149 POLYMER POLYOL AND PREFORMED STABILIZER SYSTEMS
The present invention relates to a polymer polyols and a process for the preparation thereof, and preformed stabilizer used for the preparation of polymer polyols.
Polymer polyols suitable for the preparation of polyurethane foams and elastomers are well known and are widely used on commercial scale. Polyurethane foams made from polymer polyols have a wide variety of uses. The two major types of polyurethane foams are slabstock and moulded foam . Polyurethane slabstock foams are used in carpet, furniture and bedding applications. Moulded polyurethane foams are used in the automotive industry for variety of applications.
Polymer polyols are produced by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in a polyol in the presence of a free radical catalyst to form a stable dispersion of a polymer particles in the polyol. Initially, polymer polyols producing polyurethane foams having higher load-bearing properties than those produced from unmodified polyols were prepared using acrylonitrile monomer; however, many of these polymer polyols had undesirably high viscosity.
Presently, polyurethane foams having high load-bearing properties are predominantly produced using polymer polyols which are prepared using a high styrene content monomer mixture (e.g., 65 to 75 SU~ 111 ~ITE SHEET (RULE 26) percent styrene). However, polymer polyols produced from such high styrene monomer mixture often do not satisfy the ever-increasing industry needs, including acceptable viscosity, strict stability requirements and increased load-bearing properties.
Stability and low viscosity of polymer polyols is of increasing importance to polyurethane foam manufacturers due development of sophisticated, high speed and large volume equipment and systems for handling, mixing and reacting polyurethane-forming ingredients.
Polymer polyols must meet certain minimum polymer particles size requirements to avoid filters, pumps and other parts of such foam processing equipment becoming plugged or fouled in relatively short periods of time, Numerous attempts have been made to produce polymer polyols which will meet foam processing and load-bearing properties required by polyurethane foam industry.
U.S. Patent No. 4,242,249 (Van Cleve et al) describes polymer polyols prepared by using certain preformed dispersants or stabilizers.
These polymer polyols provide stability satisfactory for commercial production, and use of at least one of (i) high amounts of styrene or other comonomer with acrylonitrile, (ii) higher solids contents or (iii) the use of lower molecular weight polyols. The particular stabilizer used and the concel ,tl dtion used vary with respect to the monomer system used in the preparation of polymer polyols.
U.S. Patent No. 4,652,589 (Simroth et al) describes stabilizer precursors for po!ymer polyols. Stabilizer A is made by reacting a 34 hydroxyl number, 15 weight percent ethylene oxide capped polyoxypropylene triol with maleic anhydride and subsequently with ethylene oxide. Stabilizer A has a hydroxyl number of 32, an unsaturation of 0.1 meq/g, with the unsaturation being 30/70 maleate/fumarate. Stabilizer B is made by reacting a 28 hydroxyl number sorbitol started polyol, containing 10 percent internal ethylene oxide, SlJ~ 111 UTE SHEET (RULE 26~
-W O 97/15605 PCT~EP95/04149 with maleic anhydride, and subsequently with propylene oxide.
Stabilizer B has a hydroxyl number of 28 and an unsaturation of approximately 0.07 meq/g, with the unsaturation being of the fumarate type.
U.S. Patent No 5,196,476 (Simroth) describes: (a) a high potency preformed stabilizer; (b) the use of same in the manufacture of polymer polyols having high solids content, lower viscosity and excellent product stability; and (c) a polyurethane made using such polymer polyol.
The preformed stabilizer is the free radical polymerization product of at least one free radically polimerizable ethylenically unsaturated monomer and at least one polyhydric alcohol adduct comprising a polyhydric alcohol residue and a residue of a compound having fumaric or maleic type unsaturation.
U.S. Patent No. 5,364,906 (Critchfield et al) describes a method for producing a stable, low viscosity polymer polyol via a modified seed method bythe steps of (1) producing a first reaction product by polymerizing a first feed in a first continuous reactor in the presence of 20 an initiator, the first feed comprising less than 50 weight percent of a total monomer proportion in at least 50 weight percent of a total base polyol proportion, optionally in the presence of a precursor stabilizer which is prepared by reacting a polyol with maleic anhydride; and (2) producing a second reaction product by polymerizing a second feed in a 25 continuous reactor in the presence of an initiator, the second feed comprising (a) the first reaction product, (b) at least 50 weight percent of the total monomer proportion, and (c) any balance of the base polyol proportion.
European Patent No. 0 1 6Z 589 B1 (Cloetens et al) describes a nonaqueous dispersion stabilizer which is the reaction product of a polyether polyol having an average molecular weight greater than 400 and a hydroxyl number in the range of 20 to 280 with silicon atom containing compound having at least least one olefinically unsaturated functional group and at least one functional group attached to the SUBSTITUTE SHEET (RULE 26) -W O 97/15605 PcT~ 5/o~l49 silicon atom which is reactable with the hydroxyl groups on the polyether polyol.
Additional prior art of interest include U.S. Patent No. Re.
32,733 (Simroth et al); U.S. Patent No.3,931,092 (Ramlow et al); U.S.
Patent No.4,014,846 (Ramlow et al); U.S. Patent No.4,093,~73 (Ramlow et al); U.S. Patent No.4,148.840 (Shah); U.S. Patent No.4,172,825 (Shook et al); U.S. Patent No.4,342,840 (Kozawa et al); U.S. Patent No.4,390,645 (Hoffman et al); U.S. Patent No. 5,394,491 (Hoffman); U.S. Patent No.
4,454,255 (Ramlow et al); U.S Patent No.4,458,038 (Ramlow et al); and U.S. Patent No.4,745,153 (Hoffman).
Although there has been progress in reduction of viscosity and increased in solids content of polymer polyols, there is still a need for polymer polyols having improved processing and load-bearing properties and for alternate method for making same.
The present invention is directed to a preformed stabilizer composition and to the manufacture of polymer polyols therewith which polymer polyols possess a combination of (a) high polymer content, from 30 weight percent to 60 weight percent, (b) lower viscosities, typically less than 9,000 centipose, (c) product stability such that 100% passes through a 150 mesh screen, and (d) up to 100% of the polymer solids content passes through a 700 mesh screen.
In one aspect, the present invention concerns a preformed stabilizer composition for use in the preparation of polymer polyols comprising the reaction product of (i) a polyol;
(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4 n or RnSi((-OSi(R1)2)pX)4 n SUBSTITUTE SHEET (RULE 2~;~
wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greaterthan zero, with a polyether polyol having an average moiecular weight in excess of 400 and a hydroxyl number in the range 20 to 280;
(iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator.
In another aspect, the present invention concerns a process for the preparation of the preformed stabilizer composition which process lS comprises providing above mentioned composition components (i), (ii), (iii) and (iv) in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time 20 sufficient to react essentially all the precursor stabilizer and recovering a heterogenous mixture containing the preformed stabilizer composition.
In another aspect, the present invention concerns a polymer polyol composition which has a polymer content of 30 to 60 weight 25 percent, based on total weight, a viscosity in centipose of not more than 8,000 and product stability such that essentially 1 Oû~/0 passes through a 150 mesh screen and up to 100% passes through a 700 mesh screen produced by a free radical polymerization of the composition comprising:~0 (a) a polyol;
(b) the above preformed stabilizer composition;
(c) at least one ethylenically unsaturated monomer;
SUBSTITUTE SHEET (RULE 26) W O 97/1~605 PCTAEP95/04149 (d) a free radical polymerization initiator; and, optionally, (e) a chain transfer agent.
In another aspect, the present invention concerns a process 5 for the preparatiPn of a polymer polyol composition which process comprises providing above mentioned polymer polyol forming composition components (a), (b), (c) and (d) in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid 10 phases in the reaction zone, for a period of time sufficient to react a major portion of the ethylenically unsaturated monomer to for a heterogenous mixture containing the polymer polyol and recovering recovering same from this heterogenous mixture.
Yet in another aspect, the present invention concerns a polymer polyol composition which possesses a polymer content of 30 to 60 weight percent, based on total weight, a viscosity in centipose of no more than 8,000 and product stability such that essentially 100% passes 20 through a 150 mesh screen produced by a free radical polymerization of the above polymer polyol forming composition.
Yet in another aspect, the present invention concerns a polyurethane foam forming composition comprising the above polymer 25 polyol composition, a polyurethane catalyst, an organic polyisocyanate, a silicone surfactant, and a blowing agent Yet in another aspect, the present invention concerns a polyurethane foam made from the above polyurethane foam forming 30 Composition~
Precursor stabilizers useful in the present invention are obtained by reacting a silicon atom containing compound of formula RnSiX4 n or RnSi((-OSi(Rl)2)pX)4 n S~ I lJTE SHEET (RULE 26) wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than 5 zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280. The particularly preferred precursor stabilizers are the reaction products of vinyltrimethoxy silane, vinyltriethoxy silane or vinyltripropoxy silane with a polyetherpolyol having an average molecular weight in excess of 400 lO and a hydroxyl number in the range 20 to 280. These precursor stabilizers and their preparation are described in European Patent No. 0 162 589 B1 (Cloetens et al).
The polyols used in the composition for preparing the 15 preformed stabilizer composition of this invention may be for example polyether polyols, polyhydroxyl containing polyesters, polyhydroxyl terminated polyurethane polymers, polyhydric polythioethers, and polytetrahydrofurans. These polyols are well known and are commercially available. The preferred polyols are the polyether polyols.
20 The polyether polyol used should have a number average molecular weight in excess of 400, preferably from 3,000, more preferably from 5,000 and a hydroxyl number in the range 20 to 280. Most preferably, the polyether polyol should be a poly (oxyethylene) (oxypropylene) adduct of 25 an alcohol selected from glycerol, trimethylolpropane, diethylene glycol, the isomers of butanetriol, pentanetriol and hexanetriol and pentaerythritol, sucrose and sorbitol. A mixture of polyols can be used, if desired. The polyol concentration in the preformed stabilizer forming composition is not critical and can be varied within wide limits. Typically, 30 the concentration can vary from 50 to 90 weight percent or even more, preferably 60 to 70 weight percent, based on the total feed to the reactor. A mixture of various useful polyols can be used, if desired.
Any ethylenically unsaturated monomer which is free radically polymerizable can be used as component (iii) in the preformed stabilizer SUBSTITUTE SHEET ~RULE 26) W O 97/15605 PCT~EP95/04149 forming cornposition of this invention. It is preferred to use vinyl monomers. Styrene, acrylonitrile, methacrylonitrile and methyl methacrylate are preferred vinyl monomers. Most preferred vinyl monomers are styrene, acrylonitrile and mixtures thereof. Typically, a minimum of 2 to 20 percent by weight of an ethylenically unsaturated 5 monomer is used in the preformed stabilizer forming composition. When a mixture of styrene and acrylonitrile is used, the weight proportion of styrene can vary from 20 to 80 weight percent and acrylonitrile can accordingly vary from 80 to 20 weight percent of the mixture. A styrene 10 to acrylonitrile ratio in the monomer mixture of from 80:20 to 20:80 is preferred, with the ratio of from 70:30 to 50: 50 being most preferred.
The free radical polymerization initiator useful in the preparation of the preformed stabilizer of this invention can be any 15 compounds which are routinely used to effect grafting of an ethylenically unsaturated polymerto a polyol including peroxides, perborates, persulphates, percarbonates and azo compounds. Typical examples of such free radical initiators include, alkyl and aryl hydroperoxides, dialkyl and diaryl peroxides, dialkylperoxydicarbonates and azobis(nitriles).
20 Preferred free radical initiators are terrt-butylperoxy diethyl acetate and tert-butyl peroctoate. The free radical initiator concentration in the preformed stabilizerforming composition is not critical and can be varied within wide limits. Typically, the concentration can vary from 0.01 to 2.0 weight percent or even more, preferably 0.05 to 0.2 weight percent, 5 based on the total feed to the reactor. The particular free radical initiator concer.l,dLion selected will usually be an optimum value considering all factors, including costs.
Typically, the polyol is used in an amount of from 50 to less 80 30 weight percent, the precursor stabilizer in an amount of from 10 to less than 50 weight percent, the monomer in an amount of from 5 to 15 weight percent and the free radical polymerization initiate in an amount of from 0.01 to 2 weight percent in the preformed stabilizer forming composition of t~is invention.
SUBSTITUTE SHEET(RULE26 -W O 97/15605 PCT~EP95/04149 The pcocess for preparing the preformed stabilizer is similar to the process for preparing the polymer polyol. The temperature ran~e is not critical and may vary from 80 ~C to 150 ~C. The preferred temperature range is from 110 ~C to 130 ~C. The mixing conditions used are those 5 obtained using a back mixed reactor. The reactors of this type keep the reaction mixture relatively homogenous and so prevent localized high monomer to precursor stabilizer ratios such as occur in tubular reactors, where all of the monomer is added at the beginning of the reactor.
The present invention also concerns the preparation of stable, high solids polymer polyols compositions which have acceptable viscosities.
The polymer polyol composition of the present invention possesses a polymer content of from 30, preferably 40, most preferably 40 weight percent, to 50 weight percent, the remainder being liquid polyol.
Over the range of solids content, it can have a viscosity in centipose less than 9,000. The polymer polyol compositions of the present invention also show exceptional stability such that essentially 100 percent passes through a 150 mesh screen and a significant amounts of high solids content polymer polyol, essentially 100 percent passes through 700 mesh screen. As shown in the examples, polymer polyol compositions having a solids content of 42.2, 45.2, 40.6 and 41.8 percent, with a viscosity of 5550, 6800, 4950 and 3280 centipose, respectively, all passed essentially 100 percent through a 700 mesh screen.
The polymer polyol composition of the present invention is the reaction product of the composition comprising: (a) a polyol; (b) the preformed stabilizer composition of the present invention; (c) at least 30 one ethylenically unsaturated monomer; and (d) a free radical polymerization initiator.
The process for preparing the polymer polyols of the present invention comprises: (1) providing a heterogenous mixture of the preformed stabilizer composition of the present invention in SlJts;~ JTE SHEET (RULE 26) W O 97/15605 PCT~EP95/04149 combination with a polyol, at least one free radically polymerizable monomer and a free radical polymerization initiator, in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization reaction, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time sufficient to react 5 a high proportion of the at least one ethylenically unsaturated monomer, and recovering the resulting polymer polyol.
~ ny known polyol having a functionality of at least tvvo and a molecular weight in excess of 400, preferably from 1,000 and 15,000, 10 more preferably from 2,00 to 8,000, and a hydroxyl number in the range 20 to 280 can be used for the preparation of polymer polyols of the present invention. These polyols are well known and are available commercially. The same or different polyol as the one used for the 15 preparation of the preformed stabilizer may be used for the preparation of the polymer polyol composition of this invention. Useful polyols may be for example polyether polyols, polyhydroxyl containing polyesters, polyhydroxyl terminated polyurethane polymers, polyhydric polythioethers, and polytetrahydrofurans. The pre~er,ed polyols are the 20 polyether polyols. Most preferably, the polyether polyol should be a poly (oxyethylene) (oxypropylene) adduct of an alcohol selected from glycerol, trimethylolpropane, diethylene glycol, the isomers of butanetriol, pentanetriol and hexanetriol and pentaerythritol. The polyol concentration in the polymer polyol forming composition is not Z5 critical and can be varied within wide limits. Typically, the concentration can vary from 40 to 80, preferably 45 to 70, more preferably from 50 to 60, weight percent, based on the total feed to the reactor. The particular polyol used will depend on the end use of the polyurethane foam to be 30 produced. A mixture of various useful polyols can be used, if desired.
Any ethylenically unsaturated monomer which is free radically polymerizable can be used as component (iii) in the preformed stabilizer forming composition of this invention. It is preferred to use vinyl monomers. Preferred vinyl monomers are styrene, acrylon;trile, methacrylonitrile and methyl methacrylate. The most preferred vinyl Sl,. ;~ JTE SHEET ~RULE 26) W O 97/15605 PCT~EP95/04149 11 monomers are styrene, acrylonitrile and mixtures thereof. Typically, a minimum of 30 to 60 percent by weight of an ethylenically unsaturated monomer is used in the preformed stabilizer forming composition. When a mixture of styrene and acrylonitrile is used, the weight proportion of styrene can vary from 80 to 20 weight percent and acrylonitrile can 5 accordingly vary from 80 to 20 weight percent of the mixture. A styrene to acrylonitrile ratio in the monomer mixture of from 80:20 to 20:80 is preferred, with the ratio of from 70:30 to 50: 50 being most preferred.
The free radical polymerization initiator useful in the lO preparation of the preformed stabilizer of this invention can be any compounds which are routinely used to effect vinyl polymerization reaction including peroxides, perborates, persulphates, percarbonates and azo compouflds. Typical examples of such free radical initiators 15 include, alkyl and aryl hydroperoxides, dialkyl and diaryl peroxides, dialkylperoxydicarbonates and azobis(nitriles). Preferred free radical initiators are 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(methylbutyro-nitrile). The free radical initiator concer,tldlion in the polymer polyol forming composition is not critical and can be varied within wide limits.
20 Typically, the concentration can vary from 0.01 to 5.0 weight percent, preferably 0.01 to 2.0 weight percent, more preferably 0.05 to 0.2 weight percent, based on the total feed to the reactor. The particular free radical initiator concentration selected will usually be an optimum value considering all factors, including costs.
If desired, any known chain transfer agent can be used in the prepolymer stabilizer forming composition of the present invention.
Preferred chain transfer agents are monohydroxy alcohols because of their ease of stripping from the final polymer polyol composition. The ~ most preferred chain transfer agent is isopropanol.
The polymer polyol forming composition is provided into the reactor, preferably a continuous, stirred, back-mixed reactor. The internal temperature of the reactor is controlled within a range of from 80 ~C to 150 ~C, preferably 110 ~C to 130 ~C. The contents of the reactor SUBSTITUTE SHEET (RULE 26) W O 97/15605 PCT~EP95/04149 12 are well mixed with the residence time of at least 5 minutes, preferably preferably from 15 to 45 minutes.
The polymer polyol composition of the present invention is useful in the preparation of polyurethane foams. Such polyurethane 5 foams have improved load-bearing and tensile strength properties without impairment of other physical properties of the foam.
The polyurethane foams are prepared by reacting the polymer polyol composition of the present invention with a polyfunctional 10 organic isocyanate in the presence of a catalyst for the urethane forming reaction, a blowing agent and a foam stabil;zer.
Polyfunctional organic isocyanates which can be used for the preparation of the polyurethane foam are well known and are available 15 commercially. Illustrative examples of useful polyfunctional organic isocyanates include the toluene diisocyanates, especially 2,4-and 2,6-toluene diisocyanate (TDI) as well as any desired mixture of these isomers; 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI) as well as any desired mixture of these isomers; oligomers of MDI (polymeric MDI), 20 polymethylene polyphenyl polyisocyanates (commonly referred to as "crude MDI"); mixtures of TDI and polymeric MDI and mixtures of the these polyisocyanates. Prepolymers of the above isocyanate (e.g. with polyether polyols, glycols or mixtures of these) can also be used in the present invention. The preferred isocyanate is 80/20 TDI (a mixture of 80 percent 2,4-toluene diisocyanate and 20 percent 2,6-toluene diisocyanate). Polyfunctional isocyanates are used in amounts well known to skilled persons.
Any of the known blowing agents conventionally used in the production of polyurethane foams can be used. Suitable blowing agents include water and halogenated hydrocarbons of low molecular weight.
The blowing agents are used in amounts well known to skilled persons.
Any of the polyurethane catalysts normally used in the preparation of polyurethane foams may be used in the process of the SUBSTITUTE SHEET (RULE ~6) present invention including tertiary amines and organometallic compounds. The polyurethane catalyst is used in amounts well known to skilled persons. Mixtures of polyurethane catalysts may also be employed in the process of the present invention.
Any of the foam stabilizers or surfactants for cell stability or other cell size control agents normally used in the preparation of polyurethane foams can be used in the present invention. The foam stabilizers, surfactants for cell stability or other cell control agents are used in amounts well known to skilled persons. Mixtures of one one or more stabilizers and/or one or more surfactants may also be used.
Suitable surfactants include the diverse silicone surfactants, preferably those which are block copolymers of a polysiloxane and a polyoxyalkylene as described in U.S. Patent 3,629,308.
Known crosslinkers may also be used in the process of the invention to modify polyurethane foam properties. These crosslinkers are used in amounts well known to skilled persons.
in addition to the above mentioned materials, any number of 20 a variety of additives conventionally used in the production of polyurethane foams such as, for example, fire retardants, defoamers, anti oxidants, mold release agents, dyes, pigments and fillers can also be used in the process of the present invention. These additives are used in 25 amounts well known to skilled persons.
The following designations, symbols, terms and abbreviations are used in the Examples below:
CP-3040 is a glycerine started polyol having hydroxyl number in the range of 54 to 59 and Average Molecular Weight of 3,000 and viscosity at 25 ~C of 490 cps, available from The Dow Chemical Company under the trademark VORANOL
CP-3040.
SUBSTITUTE SHEET (RULE 26) W O 97/15605 PCTAEP9~/04149 CP-4702 is a glycerine started polyol having hydroxyi number in the range of 33-38 and Average Molecular Weight of 4,700 and viscosity at 25 ~C of 820 cps, available from The Dow Chemical Company under the trademark VORANOL
CP-4702.
DNC-635.04 is a sorbitol started polyol having hydroxyl number of 30 and Average Molecular Weight of 7000.
VTMSP vinyltrimethoxy silane modified precursor stabilizer prepared according to Example 3 of EP-0 162 589 B1.
Trigonox 27 is a free radical polymerization initiator sold by Akzo Chemie under the trademark TRIGONOX 27.
Vazo 67 is a 2,2'-Azobis(2-methylbutanenitrile) polymerization catalyst made by E.J. duPont de Nemours and Co.
Dabco 33LV a 33 percent solution of triethylene diamine in dipropylene glycol, sold by Air Products and Chernicals Inc. under the trademark DABCO 33LV.
Niax A-107 is a formic-acid-blocked version of 70% bis(2-dimethylaminoethyl)etherl30% dipropylene glycol amine catalyst available from Union Carbide Corp. under the trademark NIAX A-107.
DEOA is Diethanolamine.
DC-5164 is a silicone surfactant sold by Dow Corning Corporation.
IPA is isopropanol.
TDI-80 is a 80:Z0 mixture of the Z,4- and 2,6-toluene diisocyanate isomers sold bythe Dow Chemical Company under the trademark Voranate T80.
SIJ~ 111 ~ITE SHEET (RULE 26) Index is the ratio of the amount of reactive isocyanate groups in the reaction mixture divided by the amount of active hydrogen groups in the reaction mixture multiplied by 100.
STN is Styrene.
ACN is Acrylonitrile.
Properties of the polymer polyol composition and 10 polyurethane foams given in the Examples below are determined according to the following test methods:
Air Flow (cfm) is measured according to the ISO 7231 test method (on AMSCOR foam porosity instrument).
Density is measured according to the DIN 53420 test method.
CFD 40% (kPa) is Compression Force Deflection determined according to DIN 53577.
IFD 25% (N) is lndentation Force Deflection 25% determined according to ASTM D-3574, Test B1 and B2.
IFD 40% (N) is lndentation Force Deflection 40% determined according to ASTM D-3574, Test B1 and B2.
IFD 65% (N) is Indentation Force Deflection 65% determined according to ASTM D-3574, Test B1 and B2.
SAG factor is Indentation Force Deflection 65% divided by Indentation Force Deflection 25%.
Tensile Strength (kPa) is determined in accordance with ASTM D-3574.
SU~;~ JTE SHEET (RULE 2~;) Elongation (%) is determined in accordance with ASTM D-3574, Test E.
Tear Strength (N/m) is determined in accordance with ASTM D-3574.
Filterability is Filtration Hindrance determined by diluting one part by weight sample (e.g. 470 9) of polymer polyol with two parts by weight anhydruous isopropanol (e.g. 960 9) to remove any viscosity-imposed limitations and using a fixed quantity of material in relation to fixed cros-sectional area of screen, such that all of the polymer polyol and isopropanol solution passes by gravitythrough a 1 50-mesh or 700-mesh screen. The 1 ~-mesh screen has a square mesh with average mesh opening of 105 microns and is a UStandard Tyler" 150 square-mesh screen. The 700-mesh screen i5 made with a Dutch twill weave. The actual screen used had a nominal opening of 30 microns. The amount of sample which passes through the screen within 3000 seconds is reported as percent, a value of 100 percent indicates that over 99 weight percent passed through the screen Viscosity is measured using a Brookfield viscometer, spindle ?~ LVVT3, speed 12, in accordance with ASTM D-4874.
The following examples are given to illustrate the invention 30 and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight.
SUBSTITUTE SH~ET(RULE26) W O 97115605 PCT~EP95/04149 PREPARATION OF PREFORMED STABILIZER
The preformed stabilizer was prepared in a continuous 5 polymerization reactor empolying a tank reactor fitted with baffles and impeller. The feed components were pumped into the reactor continuously after going through an in line mixer to assure complete mixing of the feed components before entering the reactor. The contents of the reactor were well mixed. The internal temperature of the 10 reactor was controiled to within 1 ~C. The product flowed out the top of the reactor and into a second unagitated reactor also controlled within 1~C. The product then flowed out the top of the second reactor continuously through a back pressure regulator that had been adjusted 15 to maintain at least 6~ psig pressure on both reactors. The preformed stabilizer then flowed through a cooler into a collection container. The preformed stabilizer feed compositions are shown in Tab!e 1 below.
Table 1 Example 1 2 Formulation:
CP-4702 parts 45.8 0 DNC 63~.04 parts 0 81.8 VTMSP parts 46.0 10.0 Trigonox 27 parts 0.2 0.2 STY parts 5.6 5.6 ACN parts 2.4 2.4 Sl~ 111 UTE SHEET (RULE 26) PREPARATION OF POLYMER POLYOL COMPOSITION
The polymer polyol of the present invention was prepared using a continuous polymerization system, using a tank reactor fitted with baffles and impeller. In Examples 3 to 4 and 6 to 9, the polymer 10 polyol composition feed components were pumped into the reactor continuously after going through an in line mixer to assure complete mixing of the feed components before entering the reactor. The contents of the reactor were well mixed. The internal temperature of the reactor was controlled to within 1~C. The product flowed outthe top of 15 the reactor and into a second unagitated reactor also controlled within 1 ~C. The product then flowed out the top of the second reactor continuously through a back pressure regulator that had been adjusted to give about 45 psig pressure on both reactors. The crude polymer polyol product then flowed through a cooler into a collection vessel.
20 Percent by weight polymer in the polymer polyol was determined from analysis of the amount of unreacted monomers present in the crude product. The crude product was vacuum stripped to remove volatiles before testing. The polymer polyol in Example 5 was prepared by the 25 same procedure as used in Examples 3 to 4 and 6 to 9 except that the preformed stabilizer was continuouslyfed into the polymer polyol forming reactor from the reactor it was prepared in while the rest of the polymer polyol composition feed was pumped into the same reactor. All the polymer polyols produced were stable compositions. The polymer 30 polyol feed compositions, preparation conditions and polymer polyol properties are shown in Table 2 below.
S~ S;~ ITE SHEET ~RULE 26) W O 97/15605 PCT~EP95/04149 Table 2 Example 3 4 5 6 7 8 9 Formulation:
CP-4702 parts50.6 48.3 50.3 0 44.3 49.8 50.6 CP-3040 parts 0 0 0 51.6 0 0 0 Preformed parts 3.8 3.3 3.8 3.8 6.6 4.3 o Stabilizer of Ex.1 Preformed parts 0 0 0 0 0 0 3.8 Stabilizer of Ex.2 Vazo 67 parts 0.4 0.4 0.4 0.4 0.4 0.41 0.41 STY parts24.3 26.0 24.5 28.9 24.2 24.5 24.3 ACN parts16.2 17.3 16.3 12.4 19.8 16.3 16.2 IPA parts 4.7 4.7 4.7 2.9 4.7 4.7 4.7 Prep. Conditions React. Temp. ~C 125 125 125 125 115 115 125 Monomer in total wt% 40.5 43.3 40.8 41.3 44 40.8 40.5 feed Ratio ACN/STY 40t60 40/60 40/60 30/70 45/55 40/60 40/6C
Residual STY parts0.22 0.22 1.3 1.12 0.10 0.3 0.2 Residual ACN parts0.78 0.76 1.64 0.52 0.30 0.9 0.8 Total polymer wt% 42.2 45.2 40.6 41.8 45.9 41.7 41.4 Product Properties Viscosity cps 5550 6800 4950 3280 8780 6180 5200 Filterability:
150-mesh % 100 100 100 100 100 100 100 700-mesh % 100 100 100 100 100 100 100 SIJ~ 111 ~JTE SHEET (RULE 26) W O 97/1~605 PCTrEP95/04149 PREPARATION OF POLYURETHANE FOAMS
Polyurethane foams were produced by pouring foam formulations shown in Table 3 below into an aluminum, 16 liter (40x40x10 cm), 4 vent holes mould heated to a temperature of about 60 l0 oc using Admiral high pressure pouring machine DHF-I and Krauss Maffei MK12-12/1 6-UL-2K Duplex mixing head and allowing the foam to rise and curing. The foam demould time was 5 minutes. Kluber 91 8/9K mould release agent (sold by Kluber A6) was used as the mould release agent.
15 The polyol component/isocyanate component tanks pressure was 3 bars.
Both the polyol component and isocyanate components were dispensed at about 150 bars pressure. Polymer Polyol A used in the foam formulation shown in Table 3 below is the polymer polyol produced in Example 3 herein, diluted with CP-4702 base polyol. Polymer Polyol A has 20 viscosity (at 25 ~C) of 3,000 cps and a solids content of 28 weight percent.
Polymer Polyol B used in the foam formulation shown in Table 3 below is the polymer polyol produced in Example 3 herein, diluted with CP-4702 base polyol. Polymer Polyol B has viscosity (at 25 ~C) of 3,400 cps and a solids content of 33 weight percent.Foam formulations and foam 25 properties are shown in Table 3 below. As can be seen from Table 3 below, polyurethane foams prepared in Examples 10 and 11 using a the polymer polyol of the present invention exhibit high load-bearing characteristics without any significant loss in other physical 30 characteristics.
SU~ 1 l l UTE SHEET (RULE 26) W O 97/15605 PCT/~1~ 149 Table 3 Example 10 11 Polyol Component:
Copolymer Polyol A parts 100 0 Copolymer Polyol B 0 100 water parts 3.6 3.6 DEOA (10~%) parts 1.6 1.6 Niax A-107 parts 0.Z 0.2 Dabco 33LV parts 0.2 0.2 lS DC-5164 parts 1.1 1.1 Isocyanate Component TDI-80 Index 80 80 Foam Properties:
Core Density kg/m335.4 34.8 C.F.D 40% kPa 4.11 4.86 I.F.D.25% N 127 156 I.F.D.40% N 207 251 I.F.D.65% N 449 556 I.F.D.65%/l.F.D.25% 11.61 13.96 Tensile Stréngth kPa 181 166 Elongation % 116 99 Tear Strength Ntm 328 348 SU,.~ 1 l l ~ITE SHEE~ (RULE 26)
The present invention relates to a polymer polyols and a process for the preparation thereof, and preformed stabilizer used for the preparation of polymer polyols.
Polymer polyols suitable for the preparation of polyurethane foams and elastomers are well known and are widely used on commercial scale. Polyurethane foams made from polymer polyols have a wide variety of uses. The two major types of polyurethane foams are slabstock and moulded foam . Polyurethane slabstock foams are used in carpet, furniture and bedding applications. Moulded polyurethane foams are used in the automotive industry for variety of applications.
Polymer polyols are produced by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in a polyol in the presence of a free radical catalyst to form a stable dispersion of a polymer particles in the polyol. Initially, polymer polyols producing polyurethane foams having higher load-bearing properties than those produced from unmodified polyols were prepared using acrylonitrile monomer; however, many of these polymer polyols had undesirably high viscosity.
Presently, polyurethane foams having high load-bearing properties are predominantly produced using polymer polyols which are prepared using a high styrene content monomer mixture (e.g., 65 to 75 SU~ 111 ~ITE SHEET (RULE 26) percent styrene). However, polymer polyols produced from such high styrene monomer mixture often do not satisfy the ever-increasing industry needs, including acceptable viscosity, strict stability requirements and increased load-bearing properties.
Stability and low viscosity of polymer polyols is of increasing importance to polyurethane foam manufacturers due development of sophisticated, high speed and large volume equipment and systems for handling, mixing and reacting polyurethane-forming ingredients.
Polymer polyols must meet certain minimum polymer particles size requirements to avoid filters, pumps and other parts of such foam processing equipment becoming plugged or fouled in relatively short periods of time, Numerous attempts have been made to produce polymer polyols which will meet foam processing and load-bearing properties required by polyurethane foam industry.
U.S. Patent No. 4,242,249 (Van Cleve et al) describes polymer polyols prepared by using certain preformed dispersants or stabilizers.
These polymer polyols provide stability satisfactory for commercial production, and use of at least one of (i) high amounts of styrene or other comonomer with acrylonitrile, (ii) higher solids contents or (iii) the use of lower molecular weight polyols. The particular stabilizer used and the concel ,tl dtion used vary with respect to the monomer system used in the preparation of polymer polyols.
U.S. Patent No. 4,652,589 (Simroth et al) describes stabilizer precursors for po!ymer polyols. Stabilizer A is made by reacting a 34 hydroxyl number, 15 weight percent ethylene oxide capped polyoxypropylene triol with maleic anhydride and subsequently with ethylene oxide. Stabilizer A has a hydroxyl number of 32, an unsaturation of 0.1 meq/g, with the unsaturation being 30/70 maleate/fumarate. Stabilizer B is made by reacting a 28 hydroxyl number sorbitol started polyol, containing 10 percent internal ethylene oxide, SlJ~ 111 UTE SHEET (RULE 26~
-W O 97/15605 PCT~EP95/04149 with maleic anhydride, and subsequently with propylene oxide.
Stabilizer B has a hydroxyl number of 28 and an unsaturation of approximately 0.07 meq/g, with the unsaturation being of the fumarate type.
U.S. Patent No 5,196,476 (Simroth) describes: (a) a high potency preformed stabilizer; (b) the use of same in the manufacture of polymer polyols having high solids content, lower viscosity and excellent product stability; and (c) a polyurethane made using such polymer polyol.
The preformed stabilizer is the free radical polymerization product of at least one free radically polimerizable ethylenically unsaturated monomer and at least one polyhydric alcohol adduct comprising a polyhydric alcohol residue and a residue of a compound having fumaric or maleic type unsaturation.
U.S. Patent No. 5,364,906 (Critchfield et al) describes a method for producing a stable, low viscosity polymer polyol via a modified seed method bythe steps of (1) producing a first reaction product by polymerizing a first feed in a first continuous reactor in the presence of 20 an initiator, the first feed comprising less than 50 weight percent of a total monomer proportion in at least 50 weight percent of a total base polyol proportion, optionally in the presence of a precursor stabilizer which is prepared by reacting a polyol with maleic anhydride; and (2) producing a second reaction product by polymerizing a second feed in a 25 continuous reactor in the presence of an initiator, the second feed comprising (a) the first reaction product, (b) at least 50 weight percent of the total monomer proportion, and (c) any balance of the base polyol proportion.
European Patent No. 0 1 6Z 589 B1 (Cloetens et al) describes a nonaqueous dispersion stabilizer which is the reaction product of a polyether polyol having an average molecular weight greater than 400 and a hydroxyl number in the range of 20 to 280 with silicon atom containing compound having at least least one olefinically unsaturated functional group and at least one functional group attached to the SUBSTITUTE SHEET (RULE 26) -W O 97/15605 PcT~ 5/o~l49 silicon atom which is reactable with the hydroxyl groups on the polyether polyol.
Additional prior art of interest include U.S. Patent No. Re.
32,733 (Simroth et al); U.S. Patent No.3,931,092 (Ramlow et al); U.S.
Patent No.4,014,846 (Ramlow et al); U.S. Patent No.4,093,~73 (Ramlow et al); U.S. Patent No.4,148.840 (Shah); U.S. Patent No.4,172,825 (Shook et al); U.S. Patent No.4,342,840 (Kozawa et al); U.S. Patent No.4,390,645 (Hoffman et al); U.S. Patent No. 5,394,491 (Hoffman); U.S. Patent No.
4,454,255 (Ramlow et al); U.S Patent No.4,458,038 (Ramlow et al); and U.S. Patent No.4,745,153 (Hoffman).
Although there has been progress in reduction of viscosity and increased in solids content of polymer polyols, there is still a need for polymer polyols having improved processing and load-bearing properties and for alternate method for making same.
The present invention is directed to a preformed stabilizer composition and to the manufacture of polymer polyols therewith which polymer polyols possess a combination of (a) high polymer content, from 30 weight percent to 60 weight percent, (b) lower viscosities, typically less than 9,000 centipose, (c) product stability such that 100% passes through a 150 mesh screen, and (d) up to 100% of the polymer solids content passes through a 700 mesh screen.
In one aspect, the present invention concerns a preformed stabilizer composition for use in the preparation of polymer polyols comprising the reaction product of (i) a polyol;
(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4 n or RnSi((-OSi(R1)2)pX)4 n SUBSTITUTE SHEET (RULE 2~;~
wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greaterthan zero, with a polyether polyol having an average moiecular weight in excess of 400 and a hydroxyl number in the range 20 to 280;
(iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator.
In another aspect, the present invention concerns a process for the preparation of the preformed stabilizer composition which process lS comprises providing above mentioned composition components (i), (ii), (iii) and (iv) in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time 20 sufficient to react essentially all the precursor stabilizer and recovering a heterogenous mixture containing the preformed stabilizer composition.
In another aspect, the present invention concerns a polymer polyol composition which has a polymer content of 30 to 60 weight 25 percent, based on total weight, a viscosity in centipose of not more than 8,000 and product stability such that essentially 1 Oû~/0 passes through a 150 mesh screen and up to 100% passes through a 700 mesh screen produced by a free radical polymerization of the composition comprising:~0 (a) a polyol;
(b) the above preformed stabilizer composition;
(c) at least one ethylenically unsaturated monomer;
SUBSTITUTE SHEET (RULE 26) W O 97/1~605 PCTAEP95/04149 (d) a free radical polymerization initiator; and, optionally, (e) a chain transfer agent.
In another aspect, the present invention concerns a process 5 for the preparatiPn of a polymer polyol composition which process comprises providing above mentioned polymer polyol forming composition components (a), (b), (c) and (d) in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid 10 phases in the reaction zone, for a period of time sufficient to react a major portion of the ethylenically unsaturated monomer to for a heterogenous mixture containing the polymer polyol and recovering recovering same from this heterogenous mixture.
Yet in another aspect, the present invention concerns a polymer polyol composition which possesses a polymer content of 30 to 60 weight percent, based on total weight, a viscosity in centipose of no more than 8,000 and product stability such that essentially 100% passes 20 through a 150 mesh screen produced by a free radical polymerization of the above polymer polyol forming composition.
Yet in another aspect, the present invention concerns a polyurethane foam forming composition comprising the above polymer 25 polyol composition, a polyurethane catalyst, an organic polyisocyanate, a silicone surfactant, and a blowing agent Yet in another aspect, the present invention concerns a polyurethane foam made from the above polyurethane foam forming 30 Composition~
Precursor stabilizers useful in the present invention are obtained by reacting a silicon atom containing compound of formula RnSiX4 n or RnSi((-OSi(Rl)2)pX)4 n S~ I lJTE SHEET (RULE 26) wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than 5 zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280. The particularly preferred precursor stabilizers are the reaction products of vinyltrimethoxy silane, vinyltriethoxy silane or vinyltripropoxy silane with a polyetherpolyol having an average molecular weight in excess of 400 lO and a hydroxyl number in the range 20 to 280. These precursor stabilizers and their preparation are described in European Patent No. 0 162 589 B1 (Cloetens et al).
The polyols used in the composition for preparing the 15 preformed stabilizer composition of this invention may be for example polyether polyols, polyhydroxyl containing polyesters, polyhydroxyl terminated polyurethane polymers, polyhydric polythioethers, and polytetrahydrofurans. These polyols are well known and are commercially available. The preferred polyols are the polyether polyols.
20 The polyether polyol used should have a number average molecular weight in excess of 400, preferably from 3,000, more preferably from 5,000 and a hydroxyl number in the range 20 to 280. Most preferably, the polyether polyol should be a poly (oxyethylene) (oxypropylene) adduct of 25 an alcohol selected from glycerol, trimethylolpropane, diethylene glycol, the isomers of butanetriol, pentanetriol and hexanetriol and pentaerythritol, sucrose and sorbitol. A mixture of polyols can be used, if desired. The polyol concentration in the preformed stabilizer forming composition is not critical and can be varied within wide limits. Typically, 30 the concentration can vary from 50 to 90 weight percent or even more, preferably 60 to 70 weight percent, based on the total feed to the reactor. A mixture of various useful polyols can be used, if desired.
Any ethylenically unsaturated monomer which is free radically polymerizable can be used as component (iii) in the preformed stabilizer SUBSTITUTE SHEET ~RULE 26) W O 97/15605 PCT~EP95/04149 forming cornposition of this invention. It is preferred to use vinyl monomers. Styrene, acrylonitrile, methacrylonitrile and methyl methacrylate are preferred vinyl monomers. Most preferred vinyl monomers are styrene, acrylonitrile and mixtures thereof. Typically, a minimum of 2 to 20 percent by weight of an ethylenically unsaturated 5 monomer is used in the preformed stabilizer forming composition. When a mixture of styrene and acrylonitrile is used, the weight proportion of styrene can vary from 20 to 80 weight percent and acrylonitrile can accordingly vary from 80 to 20 weight percent of the mixture. A styrene 10 to acrylonitrile ratio in the monomer mixture of from 80:20 to 20:80 is preferred, with the ratio of from 70:30 to 50: 50 being most preferred.
The free radical polymerization initiator useful in the preparation of the preformed stabilizer of this invention can be any 15 compounds which are routinely used to effect grafting of an ethylenically unsaturated polymerto a polyol including peroxides, perborates, persulphates, percarbonates and azo compounds. Typical examples of such free radical initiators include, alkyl and aryl hydroperoxides, dialkyl and diaryl peroxides, dialkylperoxydicarbonates and azobis(nitriles).
20 Preferred free radical initiators are terrt-butylperoxy diethyl acetate and tert-butyl peroctoate. The free radical initiator concentration in the preformed stabilizerforming composition is not critical and can be varied within wide limits. Typically, the concentration can vary from 0.01 to 2.0 weight percent or even more, preferably 0.05 to 0.2 weight percent, 5 based on the total feed to the reactor. The particular free radical initiator concer.l,dLion selected will usually be an optimum value considering all factors, including costs.
Typically, the polyol is used in an amount of from 50 to less 80 30 weight percent, the precursor stabilizer in an amount of from 10 to less than 50 weight percent, the monomer in an amount of from 5 to 15 weight percent and the free radical polymerization initiate in an amount of from 0.01 to 2 weight percent in the preformed stabilizer forming composition of t~is invention.
SUBSTITUTE SHEET(RULE26 -W O 97/15605 PCT~EP95/04149 The pcocess for preparing the preformed stabilizer is similar to the process for preparing the polymer polyol. The temperature ran~e is not critical and may vary from 80 ~C to 150 ~C. The preferred temperature range is from 110 ~C to 130 ~C. The mixing conditions used are those 5 obtained using a back mixed reactor. The reactors of this type keep the reaction mixture relatively homogenous and so prevent localized high monomer to precursor stabilizer ratios such as occur in tubular reactors, where all of the monomer is added at the beginning of the reactor.
The present invention also concerns the preparation of stable, high solids polymer polyols compositions which have acceptable viscosities.
The polymer polyol composition of the present invention possesses a polymer content of from 30, preferably 40, most preferably 40 weight percent, to 50 weight percent, the remainder being liquid polyol.
Over the range of solids content, it can have a viscosity in centipose less than 9,000. The polymer polyol compositions of the present invention also show exceptional stability such that essentially 100 percent passes through a 150 mesh screen and a significant amounts of high solids content polymer polyol, essentially 100 percent passes through 700 mesh screen. As shown in the examples, polymer polyol compositions having a solids content of 42.2, 45.2, 40.6 and 41.8 percent, with a viscosity of 5550, 6800, 4950 and 3280 centipose, respectively, all passed essentially 100 percent through a 700 mesh screen.
The polymer polyol composition of the present invention is the reaction product of the composition comprising: (a) a polyol; (b) the preformed stabilizer composition of the present invention; (c) at least 30 one ethylenically unsaturated monomer; and (d) a free radical polymerization initiator.
The process for preparing the polymer polyols of the present invention comprises: (1) providing a heterogenous mixture of the preformed stabilizer composition of the present invention in SlJts;~ JTE SHEET (RULE 26) W O 97/15605 PCT~EP95/04149 combination with a polyol, at least one free radically polymerizable monomer and a free radical polymerization initiator, in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization reaction, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time sufficient to react 5 a high proportion of the at least one ethylenically unsaturated monomer, and recovering the resulting polymer polyol.
~ ny known polyol having a functionality of at least tvvo and a molecular weight in excess of 400, preferably from 1,000 and 15,000, 10 more preferably from 2,00 to 8,000, and a hydroxyl number in the range 20 to 280 can be used for the preparation of polymer polyols of the present invention. These polyols are well known and are available commercially. The same or different polyol as the one used for the 15 preparation of the preformed stabilizer may be used for the preparation of the polymer polyol composition of this invention. Useful polyols may be for example polyether polyols, polyhydroxyl containing polyesters, polyhydroxyl terminated polyurethane polymers, polyhydric polythioethers, and polytetrahydrofurans. The pre~er,ed polyols are the 20 polyether polyols. Most preferably, the polyether polyol should be a poly (oxyethylene) (oxypropylene) adduct of an alcohol selected from glycerol, trimethylolpropane, diethylene glycol, the isomers of butanetriol, pentanetriol and hexanetriol and pentaerythritol. The polyol concentration in the polymer polyol forming composition is not Z5 critical and can be varied within wide limits. Typically, the concentration can vary from 40 to 80, preferably 45 to 70, more preferably from 50 to 60, weight percent, based on the total feed to the reactor. The particular polyol used will depend on the end use of the polyurethane foam to be 30 produced. A mixture of various useful polyols can be used, if desired.
Any ethylenically unsaturated monomer which is free radically polymerizable can be used as component (iii) in the preformed stabilizer forming composition of this invention. It is preferred to use vinyl monomers. Preferred vinyl monomers are styrene, acrylon;trile, methacrylonitrile and methyl methacrylate. The most preferred vinyl Sl,. ;~ JTE SHEET ~RULE 26) W O 97/15605 PCT~EP95/04149 11 monomers are styrene, acrylonitrile and mixtures thereof. Typically, a minimum of 30 to 60 percent by weight of an ethylenically unsaturated monomer is used in the preformed stabilizer forming composition. When a mixture of styrene and acrylonitrile is used, the weight proportion of styrene can vary from 80 to 20 weight percent and acrylonitrile can 5 accordingly vary from 80 to 20 weight percent of the mixture. A styrene to acrylonitrile ratio in the monomer mixture of from 80:20 to 20:80 is preferred, with the ratio of from 70:30 to 50: 50 being most preferred.
The free radical polymerization initiator useful in the lO preparation of the preformed stabilizer of this invention can be any compounds which are routinely used to effect vinyl polymerization reaction including peroxides, perborates, persulphates, percarbonates and azo compouflds. Typical examples of such free radical initiators 15 include, alkyl and aryl hydroperoxides, dialkyl and diaryl peroxides, dialkylperoxydicarbonates and azobis(nitriles). Preferred free radical initiators are 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(methylbutyro-nitrile). The free radical initiator concer,tldlion in the polymer polyol forming composition is not critical and can be varied within wide limits.
20 Typically, the concentration can vary from 0.01 to 5.0 weight percent, preferably 0.01 to 2.0 weight percent, more preferably 0.05 to 0.2 weight percent, based on the total feed to the reactor. The particular free radical initiator concentration selected will usually be an optimum value considering all factors, including costs.
If desired, any known chain transfer agent can be used in the prepolymer stabilizer forming composition of the present invention.
Preferred chain transfer agents are monohydroxy alcohols because of their ease of stripping from the final polymer polyol composition. The ~ most preferred chain transfer agent is isopropanol.
The polymer polyol forming composition is provided into the reactor, preferably a continuous, stirred, back-mixed reactor. The internal temperature of the reactor is controlled within a range of from 80 ~C to 150 ~C, preferably 110 ~C to 130 ~C. The contents of the reactor SUBSTITUTE SHEET (RULE 26) W O 97/15605 PCT~EP95/04149 12 are well mixed with the residence time of at least 5 minutes, preferably preferably from 15 to 45 minutes.
The polymer polyol composition of the present invention is useful in the preparation of polyurethane foams. Such polyurethane 5 foams have improved load-bearing and tensile strength properties without impairment of other physical properties of the foam.
The polyurethane foams are prepared by reacting the polymer polyol composition of the present invention with a polyfunctional 10 organic isocyanate in the presence of a catalyst for the urethane forming reaction, a blowing agent and a foam stabil;zer.
Polyfunctional organic isocyanates which can be used for the preparation of the polyurethane foam are well known and are available 15 commercially. Illustrative examples of useful polyfunctional organic isocyanates include the toluene diisocyanates, especially 2,4-and 2,6-toluene diisocyanate (TDI) as well as any desired mixture of these isomers; 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI) as well as any desired mixture of these isomers; oligomers of MDI (polymeric MDI), 20 polymethylene polyphenyl polyisocyanates (commonly referred to as "crude MDI"); mixtures of TDI and polymeric MDI and mixtures of the these polyisocyanates. Prepolymers of the above isocyanate (e.g. with polyether polyols, glycols or mixtures of these) can also be used in the present invention. The preferred isocyanate is 80/20 TDI (a mixture of 80 percent 2,4-toluene diisocyanate and 20 percent 2,6-toluene diisocyanate). Polyfunctional isocyanates are used in amounts well known to skilled persons.
Any of the known blowing agents conventionally used in the production of polyurethane foams can be used. Suitable blowing agents include water and halogenated hydrocarbons of low molecular weight.
The blowing agents are used in amounts well known to skilled persons.
Any of the polyurethane catalysts normally used in the preparation of polyurethane foams may be used in the process of the SUBSTITUTE SHEET (RULE ~6) present invention including tertiary amines and organometallic compounds. The polyurethane catalyst is used in amounts well known to skilled persons. Mixtures of polyurethane catalysts may also be employed in the process of the present invention.
Any of the foam stabilizers or surfactants for cell stability or other cell size control agents normally used in the preparation of polyurethane foams can be used in the present invention. The foam stabilizers, surfactants for cell stability or other cell control agents are used in amounts well known to skilled persons. Mixtures of one one or more stabilizers and/or one or more surfactants may also be used.
Suitable surfactants include the diverse silicone surfactants, preferably those which are block copolymers of a polysiloxane and a polyoxyalkylene as described in U.S. Patent 3,629,308.
Known crosslinkers may also be used in the process of the invention to modify polyurethane foam properties. These crosslinkers are used in amounts well known to skilled persons.
in addition to the above mentioned materials, any number of 20 a variety of additives conventionally used in the production of polyurethane foams such as, for example, fire retardants, defoamers, anti oxidants, mold release agents, dyes, pigments and fillers can also be used in the process of the present invention. These additives are used in 25 amounts well known to skilled persons.
The following designations, symbols, terms and abbreviations are used in the Examples below:
CP-3040 is a glycerine started polyol having hydroxyl number in the range of 54 to 59 and Average Molecular Weight of 3,000 and viscosity at 25 ~C of 490 cps, available from The Dow Chemical Company under the trademark VORANOL
CP-3040.
SUBSTITUTE SHEET (RULE 26) W O 97/15605 PCTAEP9~/04149 CP-4702 is a glycerine started polyol having hydroxyi number in the range of 33-38 and Average Molecular Weight of 4,700 and viscosity at 25 ~C of 820 cps, available from The Dow Chemical Company under the trademark VORANOL
CP-4702.
DNC-635.04 is a sorbitol started polyol having hydroxyl number of 30 and Average Molecular Weight of 7000.
VTMSP vinyltrimethoxy silane modified precursor stabilizer prepared according to Example 3 of EP-0 162 589 B1.
Trigonox 27 is a free radical polymerization initiator sold by Akzo Chemie under the trademark TRIGONOX 27.
Vazo 67 is a 2,2'-Azobis(2-methylbutanenitrile) polymerization catalyst made by E.J. duPont de Nemours and Co.
Dabco 33LV a 33 percent solution of triethylene diamine in dipropylene glycol, sold by Air Products and Chernicals Inc. under the trademark DABCO 33LV.
Niax A-107 is a formic-acid-blocked version of 70% bis(2-dimethylaminoethyl)etherl30% dipropylene glycol amine catalyst available from Union Carbide Corp. under the trademark NIAX A-107.
DEOA is Diethanolamine.
DC-5164 is a silicone surfactant sold by Dow Corning Corporation.
IPA is isopropanol.
TDI-80 is a 80:Z0 mixture of the Z,4- and 2,6-toluene diisocyanate isomers sold bythe Dow Chemical Company under the trademark Voranate T80.
SIJ~ 111 ~ITE SHEET (RULE 26) Index is the ratio of the amount of reactive isocyanate groups in the reaction mixture divided by the amount of active hydrogen groups in the reaction mixture multiplied by 100.
STN is Styrene.
ACN is Acrylonitrile.
Properties of the polymer polyol composition and 10 polyurethane foams given in the Examples below are determined according to the following test methods:
Air Flow (cfm) is measured according to the ISO 7231 test method (on AMSCOR foam porosity instrument).
Density is measured according to the DIN 53420 test method.
CFD 40% (kPa) is Compression Force Deflection determined according to DIN 53577.
IFD 25% (N) is lndentation Force Deflection 25% determined according to ASTM D-3574, Test B1 and B2.
IFD 40% (N) is lndentation Force Deflection 40% determined according to ASTM D-3574, Test B1 and B2.
IFD 65% (N) is Indentation Force Deflection 65% determined according to ASTM D-3574, Test B1 and B2.
SAG factor is Indentation Force Deflection 65% divided by Indentation Force Deflection 25%.
Tensile Strength (kPa) is determined in accordance with ASTM D-3574.
SU~;~ JTE SHEET (RULE 2~;) Elongation (%) is determined in accordance with ASTM D-3574, Test E.
Tear Strength (N/m) is determined in accordance with ASTM D-3574.
Filterability is Filtration Hindrance determined by diluting one part by weight sample (e.g. 470 9) of polymer polyol with two parts by weight anhydruous isopropanol (e.g. 960 9) to remove any viscosity-imposed limitations and using a fixed quantity of material in relation to fixed cros-sectional area of screen, such that all of the polymer polyol and isopropanol solution passes by gravitythrough a 1 50-mesh or 700-mesh screen. The 1 ~-mesh screen has a square mesh with average mesh opening of 105 microns and is a UStandard Tyler" 150 square-mesh screen. The 700-mesh screen i5 made with a Dutch twill weave. The actual screen used had a nominal opening of 30 microns. The amount of sample which passes through the screen within 3000 seconds is reported as percent, a value of 100 percent indicates that over 99 weight percent passed through the screen Viscosity is measured using a Brookfield viscometer, spindle ?~ LVVT3, speed 12, in accordance with ASTM D-4874.
The following examples are given to illustrate the invention 30 and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight.
SUBSTITUTE SH~ET(RULE26) W O 97115605 PCT~EP95/04149 PREPARATION OF PREFORMED STABILIZER
The preformed stabilizer was prepared in a continuous 5 polymerization reactor empolying a tank reactor fitted with baffles and impeller. The feed components were pumped into the reactor continuously after going through an in line mixer to assure complete mixing of the feed components before entering the reactor. The contents of the reactor were well mixed. The internal temperature of the 10 reactor was controiled to within 1 ~C. The product flowed out the top of the reactor and into a second unagitated reactor also controlled within 1~C. The product then flowed out the top of the second reactor continuously through a back pressure regulator that had been adjusted 15 to maintain at least 6~ psig pressure on both reactors. The preformed stabilizer then flowed through a cooler into a collection container. The preformed stabilizer feed compositions are shown in Tab!e 1 below.
Table 1 Example 1 2 Formulation:
CP-4702 parts 45.8 0 DNC 63~.04 parts 0 81.8 VTMSP parts 46.0 10.0 Trigonox 27 parts 0.2 0.2 STY parts 5.6 5.6 ACN parts 2.4 2.4 Sl~ 111 UTE SHEET (RULE 26) PREPARATION OF POLYMER POLYOL COMPOSITION
The polymer polyol of the present invention was prepared using a continuous polymerization system, using a tank reactor fitted with baffles and impeller. In Examples 3 to 4 and 6 to 9, the polymer 10 polyol composition feed components were pumped into the reactor continuously after going through an in line mixer to assure complete mixing of the feed components before entering the reactor. The contents of the reactor were well mixed. The internal temperature of the reactor was controlled to within 1~C. The product flowed outthe top of 15 the reactor and into a second unagitated reactor also controlled within 1 ~C. The product then flowed out the top of the second reactor continuously through a back pressure regulator that had been adjusted to give about 45 psig pressure on both reactors. The crude polymer polyol product then flowed through a cooler into a collection vessel.
20 Percent by weight polymer in the polymer polyol was determined from analysis of the amount of unreacted monomers present in the crude product. The crude product was vacuum stripped to remove volatiles before testing. The polymer polyol in Example 5 was prepared by the 25 same procedure as used in Examples 3 to 4 and 6 to 9 except that the preformed stabilizer was continuouslyfed into the polymer polyol forming reactor from the reactor it was prepared in while the rest of the polymer polyol composition feed was pumped into the same reactor. All the polymer polyols produced were stable compositions. The polymer 30 polyol feed compositions, preparation conditions and polymer polyol properties are shown in Table 2 below.
S~ S;~ ITE SHEET ~RULE 26) W O 97/15605 PCT~EP95/04149 Table 2 Example 3 4 5 6 7 8 9 Formulation:
CP-4702 parts50.6 48.3 50.3 0 44.3 49.8 50.6 CP-3040 parts 0 0 0 51.6 0 0 0 Preformed parts 3.8 3.3 3.8 3.8 6.6 4.3 o Stabilizer of Ex.1 Preformed parts 0 0 0 0 0 0 3.8 Stabilizer of Ex.2 Vazo 67 parts 0.4 0.4 0.4 0.4 0.4 0.41 0.41 STY parts24.3 26.0 24.5 28.9 24.2 24.5 24.3 ACN parts16.2 17.3 16.3 12.4 19.8 16.3 16.2 IPA parts 4.7 4.7 4.7 2.9 4.7 4.7 4.7 Prep. Conditions React. Temp. ~C 125 125 125 125 115 115 125 Monomer in total wt% 40.5 43.3 40.8 41.3 44 40.8 40.5 feed Ratio ACN/STY 40t60 40/60 40/60 30/70 45/55 40/60 40/6C
Residual STY parts0.22 0.22 1.3 1.12 0.10 0.3 0.2 Residual ACN parts0.78 0.76 1.64 0.52 0.30 0.9 0.8 Total polymer wt% 42.2 45.2 40.6 41.8 45.9 41.7 41.4 Product Properties Viscosity cps 5550 6800 4950 3280 8780 6180 5200 Filterability:
150-mesh % 100 100 100 100 100 100 100 700-mesh % 100 100 100 100 100 100 100 SIJ~ 111 ~JTE SHEET (RULE 26) W O 97/1~605 PCTrEP95/04149 PREPARATION OF POLYURETHANE FOAMS
Polyurethane foams were produced by pouring foam formulations shown in Table 3 below into an aluminum, 16 liter (40x40x10 cm), 4 vent holes mould heated to a temperature of about 60 l0 oc using Admiral high pressure pouring machine DHF-I and Krauss Maffei MK12-12/1 6-UL-2K Duplex mixing head and allowing the foam to rise and curing. The foam demould time was 5 minutes. Kluber 91 8/9K mould release agent (sold by Kluber A6) was used as the mould release agent.
15 The polyol component/isocyanate component tanks pressure was 3 bars.
Both the polyol component and isocyanate components were dispensed at about 150 bars pressure. Polymer Polyol A used in the foam formulation shown in Table 3 below is the polymer polyol produced in Example 3 herein, diluted with CP-4702 base polyol. Polymer Polyol A has 20 viscosity (at 25 ~C) of 3,000 cps and a solids content of 28 weight percent.
Polymer Polyol B used in the foam formulation shown in Table 3 below is the polymer polyol produced in Example 3 herein, diluted with CP-4702 base polyol. Polymer Polyol B has viscosity (at 25 ~C) of 3,400 cps and a solids content of 33 weight percent.Foam formulations and foam 25 properties are shown in Table 3 below. As can be seen from Table 3 below, polyurethane foams prepared in Examples 10 and 11 using a the polymer polyol of the present invention exhibit high load-bearing characteristics without any significant loss in other physical 30 characteristics.
SU~ 1 l l UTE SHEET (RULE 26) W O 97/15605 PCT/~1~ 149 Table 3 Example 10 11 Polyol Component:
Copolymer Polyol A parts 100 0 Copolymer Polyol B 0 100 water parts 3.6 3.6 DEOA (10~%) parts 1.6 1.6 Niax A-107 parts 0.Z 0.2 Dabco 33LV parts 0.2 0.2 lS DC-5164 parts 1.1 1.1 Isocyanate Component TDI-80 Index 80 80 Foam Properties:
Core Density kg/m335.4 34.8 C.F.D 40% kPa 4.11 4.86 I.F.D.25% N 127 156 I.F.D.40% N 207 251 I.F.D.65% N 449 556 I.F.D.65%/l.F.D.25% 11.61 13.96 Tensile Stréngth kPa 181 166 Elongation % 116 99 Tear Strength Ntm 328 348 SU,.~ 1 l l ~ITE SHEE~ (RULE 26)
Claims (10)
1. A polymer polyol composition which has a polymer content of 30 to 60 weight percent, based on total weight, a viscosity in centipose of not more than9,000 and product stability such that essentially 100% passes through a 150 meshscreen and up to 100% passes through a 700 mesh screen produced by a free radical polymerization of the composition comprising:
(a) a polyol;
(b) a preformed stabilizer comprising the reaction product of (i) a polyol;(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((-OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280; (iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator;
(c) at least one ethylenically unsaturated monomer;
(d) a free radical polymerization initiator; and, optionally, (e) a chain transfer agent.
(a) a polyol;
(b) a preformed stabilizer comprising the reaction product of (i) a polyol;(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((-OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280; (iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator;
(c) at least one ethylenically unsaturated monomer;
(d) a free radical polymerization initiator; and, optionally, (e) a chain transfer agent.
2. A polymer polyol composition as claimed in Claim 1, wherein the at least one ethylenically unsaturated monomer is a mixture of acrylonitrile and styrene.
3. A polymer polyol composition as claimed in Claim 2, wherein acrylonitrile and styrene are present in the mixture in the ratio of from 20:80 to 80:20.
4. A process for the preparation of polymer polyol composition which process comprises providing a composition comprising:
(a) a polyol;
(b) a preformed stabilizer comprising the reaction product of (i) a polyol;(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((-OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280; (iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator;
(c) at least one ethylenically unsaturated monomer, (d) a free radical polymerization initiator, and, optionally, (e) a chain transfer agent in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time sufficient to react essentially at least major portion of the at least one ethylenically unsaturated monomer and recovering the polymerpolyol.
(a) a polyol;
(b) a preformed stabilizer comprising the reaction product of (i) a polyol;(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((-OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280; (iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator;
(c) at least one ethylenically unsaturated monomer, (d) a free radical polymerization initiator, and, optionally, (e) a chain transfer agent in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time sufficient to react essentially at least major portion of the at least one ethylenically unsaturated monomer and recovering the polymerpolyol.
5. A process according to Claim 4, wherein the reaction zone is maintained at the temperature of from 80°C to 150°C.
6. A composition for the preparation of a polyurethane foam wherein there is used polymer polyol, a polyurethane catalyst, an organic polyisocyanate, a surfactant, and a blowing agent, characterized in that the polymer polyol comprises polymer polyol as claimed in any one of Claims 1 to 3.
7. A polyurethane foam prepared from a composition as claimed in Claim 6.
8. A polyurethane foam prepared from a polymer polyol composition as claimed in any one of Claims 1 to 3.
9. Use of a composition comprising the reaction product of (i) a polyol;(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((-OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280; (iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator as a preformed dispersion stabilizer in the polymer polyol composition which has a polymer content of 30 to 60 weight percent, based on total weight, a viscosity in centipose of not more than 9,000 and product stability such that essentially 100% passes through a 150 mesh screen and up to 100%
passes through a 700 mesh screen, which polymer polyol composition is produced by polymerizing a polyol, the above preformed dispersion stabilizer and at least one ethylenically unsaturated monomer in the presence of free radical polymerizationinitiator and, optional chain transfer agent.
passes through a 700 mesh screen, which polymer polyol composition is produced by polymerizing a polyol, the above preformed dispersion stabilizer and at least one ethylenically unsaturated monomer in the presence of free radical polymerizationinitiator and, optional chain transfer agent.
10. Use of a composition comprising the reaction product of (i) a polyol;(ii) a precursor stabilizer obtainable by reacting a silicon atom containing compound of formula RnSiX4-n or RnSi((-OSi(R1)2)pX)4-n wherein the R groups are independently saturated or unsaturated hydrocarbyl groups, at least one R group being an olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3 and p is an integer greater than zero, with a polyether polyol having an average molecular weight in excess of 400 and a hydroxyl number in the range 20 to 280; (iii) at least one ethylenically unsaturated monomer which is copolymerizable with the precursor stabilizer; and (iv) a free radical polymerization initiator as a preformed dispersion stabilizer in a process for the preparation of a polymer polyol composition which process comprises providing a polyol, said preformed dispersion stabilizer, at least one ethylenically unsaturated monomer; a free radical polymerization initiator; and, optionally, (e) a chain transfer agent in a reaction zone maintained at a temperature sufficient to initiate a free radical polymerization, and under sufficient pressure to maintain only liquid phases in the reaction zone, for a period of time sufficient to react essentially at least major portion of the at least one ethylenically unsaturated monomer and recovering thepolymer polyol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002233472A CA2233472A1 (en) | 1995-10-23 | 1995-10-23 | Polymer polyol and preformed stabilizer systems |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002233472A CA2233472A1 (en) | 1995-10-23 | 1995-10-23 | Polymer polyol and preformed stabilizer systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2233472A1 true CA2233472A1 (en) | 1997-05-01 |
Family
ID=4162263
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002233472A Abandoned CA2233472A1 (en) | 1995-10-23 | 1995-10-23 | Polymer polyol and preformed stabilizer systems |
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| Country | Link |
|---|---|
| CA (1) | CA2233472A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154095A (en) * | 2020-01-14 | 2020-05-15 | 万华化学集团股份有限公司 | Silicon modified macromolecular monomer stabilizer and preparation method and application thereof |
-
1995
- 1995-10-23 CA CA002233472A patent/CA2233472A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154095A (en) * | 2020-01-14 | 2020-05-15 | 万华化学集团股份有限公司 | Silicon modified macromolecular monomer stabilizer and preparation method and application thereof |
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