CN1778829A - Dispersion stabilizer made from vinyl trialkyl oxysilane and used for polymer popyalcohol preparation - Google Patents
Dispersion stabilizer made from vinyl trialkyl oxysilane and used for polymer popyalcohol preparation Download PDFInfo
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- CN1778829A CN1778829A CNA2005101202035A CN200510120203A CN1778829A CN 1778829 A CN1778829 A CN 1778829A CN A2005101202035 A CNA2005101202035 A CN A2005101202035A CN 200510120203 A CN200510120203 A CN 200510120203A CN 1778829 A CN1778829 A CN 1778829A
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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
- C08G18/48—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
- C08G18/08—Processes
- C08G18/16—Catalysts
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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
- C08G18/58—Epoxy resins
- C08G18/588—Epoxy resins having silicon
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- 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
- C08G18/61—Polysiloxanes
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- 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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Abstract
The invention discloses a dispersion stabilizer for preparing polymer polyalcohol. The polymer polyalcohol prepared by the dispersion stabilizer is used for preparing improved polyurethane foam. The dispersion stabilizer is prepared by the reaction of polyalcohol having functionality degree of 4.5 to 8 and molecular weight of 5,000 to 15,000 and vinyl trialkoxysilane. The polymer polyalcohol prepared by using the dispersion stabilizer has low viscosity and can help to improve physical property of the obtained polyurethane.
Description
Background of invention
Invention field
The present invention relates to be used for the dispersion stabilizer of polymer polyatomic alcohol (polyol) preparation, more specifically, the present invention relates to that to have average functionality be that 4.5-8.0 and molecular weight are 5 by making, 000-15,000 polyvalent alcohol and vinyltriethoxysilane react and the stablizer that is used for the polymer polyatomic alcohol preparation of acquisition.
Background of related
The main application of the urethane foam that is made by polymer polyatomic alcohol roughly is divided into two classes: soft board material and soft mold.Plate is used as the mat of mattress, furniture and sofa etc., and soft mold is used for each purposes, comprises automobile board and snubber.The polymer polyatomic alcohol that is fit to this urethane foam requires highly filled and low viscosity character.
Polymkeric substance/polyhydric alcohol composition is well known in the art, and is described in detail in U.S. Patent number 3,383 about their polymeric basic skills, 351 and 3,304,273.In these preparation of compositions processes, be dissolved in one or more unsaturated monomers (for example vinylbenzene, the vinyl cyanide etc.) polymerization in the presence of free radical catalyst in the polyvalent alcohol, the polymer particle that forms by polyreaction stably is dispersed in the liquid polyol.Urethane foam by these polymer polyatomic alcohol preparations has hardness and the physical properties higher than conventional porous plastics.
Initial business-like polymer polyatomic alcohol is made as reaction monomers by independent vinyl cyanide or styrene-propene mixture of nitriles.The polymer polyatomic alcohol that obtains by this monomer polymerization is used in the limited purposes, and this is because they have high viscosity, the face light yellow complexion, and on the gained urethane foam, cause the incipient scorch phenomenon.In the minimized trial of incipient scorch phenomenon that makes urethane foam, proposed styrene content is increased to the method for 65-70%.But because the increase of styrene content, this method has caused that the stability of polymer polyatomic alcohol sharply descends and the zooming problem of polyvalent alcohol viscosity.
U.S. Patent number 4,208,314 disclose the low viscosity polymer polyvalent alcohol by the preparation of styrene/acrylonitrile mixture.This patent is described, and prepared polymer polyatomic alcohol has high relatively styrene content, and the incipient scorch phenomenon of urethane foam reduces.In addition, U.S. Patent number 4,148,314 disclose the method that a kind of preparation has the polymer polyatomic alcohol of high dispersion stability and filterableness, and described method is carried out in the polyreaction of polymer polyatomic alcohol by adding a small amount of prepolymerized polymer polyatomic alcohol.
In order to prepare urethane, carried out improving the trial of polymer polyatomic alcohol with higher improvement physical properties.Particularly, in order to prepare the low viscosity polymer polyvalent alcohol that not only has the high polymers solids content but also have the stable polymer dispersion, proposed to introduce the method for the particular components that is called as " NAD (non-aqueous dispersion agent) stablizer ".The NAD stablizer obtains by following manner: introduce a small amount of degree of unsaturation in polyvalent alcohol, to increase gained solid dispersion stabilization.
U.S. Patent number 4,454,255 and 4,458,038 discloses the use of stablizer, and described stablizer is by making polyvalent alcohol and having the compound of active degree of unsaturation such as maleic anhydride or fumaric acid and react and obtain.In addition, U.S. Patent number 4,460,715 disclose with acrylate or methacrylic ester and have prepared stablizer as active unsaturated monomer.
United States Patent (USP) 4,550,194 disclose the method for preparing stablizer, wherein in the presence of the catalyzer in being selected from calcium naphthenate and cobalt naphthenate, to be that the polyvalent alcohol of 4 tetramethylolmethane preparation reacts with maleic anhydride with the OH functionality, make the carboxylic acid structure and oxirane such as oxyethane or the propylene oxide reaction that make.Analogous cases are shown in U.S. Patent number 4,998,857, wherein following steps and United States Patent (USP) 4,550, in 194 much at one: make the reaction of polyvalent alcohol and maleic anhydride to introduce degree of unsaturation, make the reaction of product and oxirane then, but at U.S. Patent number 4,998, in 857, with the OH functionality greater than 4 high molecular weight polyols (OH functionality as be shown in the examples is 6 sorbyl alcohol) as stablizer.In addition, for the synthesizing stable agent, another example of introducing the reactant of degree of unsaturation in polyvalent alcohol is that " TMI " (1-(tertiary butyl-isocyanato-(isocyanato))-3-isopropenylbenzene is as U.S. Patent number 5,494,957,4,954,561,4,954,560 and 5,093, described in 412.U.S. Patent number 4,390,645 disclose the stablizer by the preparation of 2-ethyl isocyanate ylmethyl acrylate.
European patent number 0,162,589 disclose a kind of method for preparing the non-aqueous dispersions stablizer, to have molecular-weight average be 3 to described method by making, 000-5,000 and functionality be that 3 polyether polyol and vinyl trialkyl oxysilane react and carry out.U.S. Patent number 5,990,185 disclose a kind of dispersion stabilizer, described dispersion stabilizer prepares in the following way: use the OH functionality greater than 4 high molecular weight polyols (using the OH functionality is 6 the sorbyl alcohol starting material as polyvalent alcohol) preparation preformed stabilizers, make this stabiliser precursor and a small amount of (polymer content of 5-10wt%) ethylenically unsaturated monomers polymerization then.U.S. Patent number 4,871,735 disclose a kind of dispersion stabilizer that makes by the following method: make compound with thiol such as thiol propyl trimethoxy silicane with have functionality be 3 and molecular-weight average be about 4,000 polyether polyol reaction.
The problem of using maleic anhydride to prepare the method for stablizer is, because the reaction times of maleic anhydride and oxirane is 15-32 hour, this makes the treatment time very long, and specified active unsaturated isocyanate self is very expensive as " TMI " (1-(tertiary butyl-isocyanato-)-3-isopropenylbenzene or 2-ethyl isocyanate ylmethyl acrylate).For this reason, carried out making the minimized trial of addition of the required stablizer of preparation polymer polyatomic alcohol.
U.S. Patent number 4,954,561 and 5,494,957 disclose the steric stabilization degree methods that increases stablizer, and described method is undertaken by the size that linked reaction increases the polyol moiety of stablizer molecule.At U.S. Patent number 4,954, in 561, linked reaction is undertaken by the oxalic acid coupling that makes polyvalent alcohol and oxalate diester, and at U.S. Patent number 5,494, and in 957, the coupling of stablizer is by carrying out with di-isocyanate reaction.But these coupling methods need other reaction process, cause the increase of raw materials cost and processing cost.
Therefore, need a kind of dispersion stabilizer always, described dispersion stabilizer can be in the short relatively treatment time, do not needing to prepare under other process such as the link coupled situation, and described dispersion stabilizer just can provide improved physical properties such as dispersion stabilization, filterableness and low viscosity to polymer polyatomic alcohol with less amount simultaneously.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of new dispersion stabilizer that is used to prepare polymer polyatomic alcohol.
Another object of the present invention provides a kind of dispersion stabilizer that is used to prepare polymer polyatomic alcohol, described dispersion stabilizer can prepare in the short relatively treatment time, just can provide improved physical properties such as dispersion stabilization, filterableness and low viscosity to polymer polyatomic alcohol with less amount simultaneously.
Another purpose of the present invention provides the method that a kind of preparation is used for the dispersion stabilizer of polymer polyatomic alcohol preparation.
Also purpose of the present invention is to use described stablizer to provide to have highly filled and polymer polyatomic alcohol low viscosity character.
Another object of the present invention is to use described polymer polyatomic alcohol to provide to have the more urethane foam of high rigidity and physical properties.
To achieve these goals, the invention provides a kind of new dispersion stabilizer that is used to prepare polymer polyatomic alcohol, to have average functionality be that 4.5-8.0 and molecular-weight average are 5 to described dispersion stabilizer by making, 000-15,000 polyvalent alcohol and vinyl trialkyl oxysilane react and make.
In the present invention, the polyvalent alcohol that is used to prepare the dispersion stabilizer that uses in the polymer polyatomic alcohol preparation is 5 for having average functionality as 4.5-8 and molecular-weight average, 000-15,000 polyether polyol.
The polyether polyol that uses among the present invention obtains by the following method: make polyhydroxy-alcohol (polyhydric alcohol) or its combination and oxirane reaction, having average functionality with preparation is that 4.5-8.0 and molecular-weight average are 5,000-15,000 polyvalent alcohol.Can be used for obtaining to have average functionality is that 4.5-8.0 and molecular-weight average are 5,000-15, and the example of the polyhydroxy-alcohol of 000 polyvalent alcohol comprises: ethylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol, sugar and their mixture.The mixture of preferred sugar, sugar and glycerol mixture, sorbyl alcohol or sugar and tetramethylolmethane.According to the character of gained urethane foam, the oxirane that reacts with polyhydroxy-alcohol can be selected from suitably: oxyethane, propylene oxide, butylene oxide ring, amylene oxide and their mixture.The mixture of optimization ethylene oxide and propylene oxide.
If use the average functionality polyvalent alcohol lower than above-mentioned scope, the steric hindrance of dispersions obtained stablizer will reduce, and the viscosity of polymer polyatomic alcohol will increase.On the other hand, if use the average functionality polyvalent alcohol higher than above-mentioned scope, the viscosity of gained stablizer will increase, and raw materials cost will increase.
If use the molecular-weight average polyvalent alcohol lower than above-mentioned scope, the steric hindrance of dispersions obtained stablizer will reduce, and the viscosity of polymer polyatomic alcohol will increase.On the other hand, if use the molecular-weight average polyvalent alcohol higher than above-mentioned scope, the viscosity of gained stablizer will increase, and raw materials cost will increase.
In the present invention, in order to introduce unsaturated group, having average functionality is that 4.5-8.0 and molecular-weight average are 5,000-15,000 polyether polyol can with have can with the silicone compounds reaction of the group of hydroxyl groups reaction.The preferred example of silicone compounds comprises: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane and their mixture.
On the other hand, the invention provides the polymer polyatomic alcohol that shows highly filled and low viscosity character, described polymer polyatomic alcohol makes by making unsaturated monomer in the polyvalent alcohol carry out radical polymerization in the presence of dispersion stabilizer.
In enforcement of the present invention, the example that can be used in the polyvalent alcohol in the polymerization of polymer polyatomic alcohol comprises: polyether polyol, contain polyhydric polyether polyol, the end capped polyether polyols with reduced unsaturation of poly-hydroxy, polyhydroxy polycarboxylic thioether and polytetrahydrofuran.Can comprise by raw-material example used in this invention: ethylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol and sugar.
The example that can be used for the ethylenically unsaturated monomers of polymer polyatomic alcohol preparation suitably comprises: vinylbenzene, vinyl cyanide and alpha-methyl styrene.The mixture of optimization styrene and vinyl cyanide, vinylbenzene and vinyl cyanide were with 20: 80 to 80: 20 mixed in molar ratio.Based on the gross weight of polymer polyatomic alcohol product, the consumption of ethylenically unsaturated monomers is 30-60wt%, preferred 30-50wt%.
Monomeric polymerization is undertaken by radical polymerization initiator.Based on monomeric gross weight, the consumption of this initiator is generally 0.01-1wt%.The suitable example of polymerization starter comprises peroxide compound and azo-compound.
Chain-transfer agent can be added in the polymerisation medium on a small quantity or is present in the polymerisation medium.The chain-transfer agent may command allows crosslinked between the various polymer molecules, and the stability of impact polymer polyvalent alcohol thus.Based on the gross weight of reactant, the consumption of chain-transfer agent is preferably 0.1-6wt%, more preferably 0.2-5wt%.The suitable example of chain-transfer agent comprises: 1-butanols, 2-butanols, Virahol, ethanol, methyl alcohol, water, hexanaphthene, mercaptan (for example, dodecyl mercaptans, sulfur alcohol, 1-heptanthiol, 2-spicy thioalcohol and beneze methane thiol), toluene and ethylbenzene.
In addition, polymer polyatomic alcohol of the present invention is fit to the preparation urethane foam, and described urethane foam is by making polymer polyatomic alcohol and isocyanate reaction in the presence of suitable catalysts for polyurethanes, pore forming material and linking agent.
The example that is used for the multifunctional organic isocyanate of urethane foam preparation comprises: toluene diisocyanate, especially 2,4-and 2,6-tolylene diisocyanate (TDI) and these mixture of isomers of choosing wantonly; 2,4-and 4,4-diphenylmethanediisocyanate (MDI) and its optional mixture; The oligopolymer of MDI (polymerisable MDI); Mixture with TDI and polymerisable MDI.Preferred isocyanic ester is 2 of 80% 2,4 toluene diisocyanate and 20%, the mixture of 6-tolylene diisocyanate (80/20 TDI).
In the preparation of urethane foam, can use any conventional pore forming material.The suitable example of pore forming material comprises: water, acetone, carbonic acid gas, halohydrocarbon, aliphatic alkanes and naphthenic hydrocarbon.As known in the art, make water as pore forming material by generating carbonic acid gas as pore forming material with isocyanate reaction.Aliphatic alkanes and naphthenic hydrocarbon are developed the alternative pore forming material as the CFC compound.The example of these compounds comprises: pentane, hexane, pentamethylene and hexanaphthene.Pore forming material can be used alone or use with its two or more mixture.For water, the consumption of pore forming material is 0.1-5 weight part (pbw), for other pore forming materials, is about 1-20 weight part.
In the preparation of urethane foam, can use any catalysts, its example comprises tertiary amine and organometallic compound.Based on the weight of polyvalent alcohol, catalyst consumption is generally about 0.1-3 weight part.
In the preparation of urethane foam, can use any stablizer or tensio-active agent to control the stability or the size of abscess.The suitable example of tensio-active agent comprises various silicone surfactants, the segmented copolymer of preferred polysiloxane and polyoxyalkylene.
Linking agent also can be used for improving the character of urethane foam.The common examples of linking agent comprises glycerine and diethanolamine, and the consumption of linking agent is less than 3pbw or about 0.2-1.5pbw.
Except additive above-mentioned, other various additives of using in the urethane foam preparation also can be used for the present invention.The example of these additives comprises: fire retardant, defoamer, antioxidant, releasing agent, dyestuff, pigment and filler.
DESCRIPTION OF THE PREFERRED
Hereinafter, will describe the present invention in detail by embodiment.But, should be appreciated that these embodiment provide just to the illustrative purpose, should not be construed as and limit the scope of the invention.In addition, it will be apparent to one skilled in the art that under the situation of disclosed invention scope and spirit in not deviating from, can carry out various modifications, interpolation and replacement the present invention as the accessory claim book.
Embodiment
Among the postpose embodiment of following title, abbreviation and term.
Polyvalent alcohol A: by making starting material sugared and the mixture of glycerine and the polyvalent alcohol that propylene oxide and reacting ethylene oxide prepare.OH number: 28.5; Average functionality: 7; Molecular-weight average: 13,800; Viscosity: 2,000cps/25 ℃.
Polyvalent alcohol B: by the polyvalent alcohol that starting material sorbyl alcohol and propylene oxide and reacting ethylene oxide are prepared.OH number: 42; Molecular-weight average: 8,000; Viscosity: 1,300cps/25 ℃.
Polyvalent alcohol C: by the polyvalent alcohol that starting material glycerine and propylene oxide and reacting ethylene oxide are prepared.OH number: 56; Molecular-weight average: 3,000; Viscosity: 450cps/25 ℃.
Polyvalent alcohol D: by the polyvalent alcohol that starting material glycerine and propylene oxide and reacting ethylene oxide are prepared.OH number: 34; Molecular-weight average: 4,950; Viscosity: 750cps/25 ℃.
Polyol E: by the polyvalent alcohol that starting material glycerine and independent propylene oxide reaction are prepared.OH number: 56; Molecular-weight average: 3,000; Viscosity: 450cps/25 ℃.
VTMS: vinyltrimethoxy silane
VTES: vinyltriethoxysilane
Vazo-67:2,2 '-two (2-methylbutyronitrile) polymerizing catalysts of azo (making) by E.J.du Pont deNemours and Co.;
SM: styrene monomer;
AN: vinyl cyanide;
EB: ethylbenzene;
The character of the polymer polyatomic alcohol is in the following embodiments measured according to following testing method.
OH number: the milligram number of the KOH suitable (remaining Tetra hydro Phthalic anhydride usefulness KOH solution titration after with excessive Tetra hydro Phthalic anhydride/pyridine solution esterification with the hydroxy radical content of a gram in the polyvalent alcohol; Method according to ASTM D 4274-94 is measured);
Viscosity: use Brookfield viscometer (axle #LVVT3, speed 12) to measure according to ASTM D-4874.
Embodiment 1: dispersion stabilizer (SB1) synthetic
With 1,000g polyvalent alcohol A pack into be furnished with agitator, in the reactor of thermometer and condenser.After 30 minutes material temperature in the reactor is reduced to 60 ℃ in dehumidifying under 100 ℃.VTMS joins in the reactor content with 16.6 grams (16.6 gram).Temperature of reaction rises to 140 ℃.Mixture reacted in nitrogen atmosphere 8 hours, was cooled to room temperature then.The dispersion stabilizer of gained is colourless, has 3 under 25 ℃, the viscosity of 200cps and 0.169 degree of unsaturation.
Embodiment 2-10 (SC2-10)
Prepare dispersion stabilizer in the mode identical, except the kind of polyvalent alcohol and the amount of amount and VTMS and VTES change, as shown in following table 1 with embodiment 1.
Table 1: the embodiment 1-10 that is used for synthetic dispersion stabilizer
| Polyvalent alcohol A (g) | Polyvalent alcohol B (g) | Polyvalent alcohol C (g) | VTMS (g) | VTES (g) | Degree of unsaturation (meq/g) | Viscosity (cps/25 ℃) | |
| SC1 | 1,000 | - | - | 16.6 | - | 0.169 | 3,500 |
| SC2 | 1,000 | - | - | 19.2 | - | 0.178 | 4,900 |
| SC3 | 1,000 | - | - | - | 12.0 | 0.165 | 3,700 |
| SC4 | 1,000 | - | - | - | 15.6 | 0.171 | 5,300 |
| SC5 | - | 1,000 | - | 16.6 | - | 0.173 | 2,200 |
| SC6 | - | 1,000 | - | 19.2 | - | 0.168 | 3,600 |
| SC7 | - | 1,000 | - | - | 12.0 | 0.162 | 2,300 |
| SC8 | - | 1,000 | - | - | 15.6 | 0.189 | 3,900 |
| SC9 | - | - | 1,000 | 16.6 | - | 0.175 | 770 |
| SC10 | - | - | 1,000 | 19.2 | - | 0.165 | 1,700 |
Synthesizing of comparative example 1 dispersion stabilizer
For with the present invention relatively, with U.S. Patent number 4,723, identical mode prepares stablizer among 026 the embodiment 3.
Specific descriptions are, will have the OH number and be 3 and molecular weight be 5,000 798g (0.170mol) polyvalent alcohol pack into be furnished with agitator, in 1 liter of reactor of thermometer and condenser.Dehumidifying is after 30 minutes down at 100 ℃, and material temperature is reduced to 60 ℃ in the reactor.16.6 gram (0.112mol) VTMS are added in the reactor content.Temperature of reaction rises to 140 ℃.Mixture reacted 8 hours in nitrogen atmosphere, was cooled to room temperature then.The dispersion stabilizer of gained is colourless, has the viscosity of 840cps and 0.186 degree of unsaturation under 20 ℃.
Embodiment 11: the preparation of polymer polyatomic alcohol (POP 11)
180g polyvalent alcohol and 180g EB packed into be furnished with agitator, in 3 liter of four neck reactor of condenser, thermometer and filling tube.Use polyvalent alcohol D as polyvalent alcohol.Independently, prepare feed composition by mixing 360g SM, 360g AN, 846g polyvalent alcohol, 2.72g dispersion stabilizer (SC 2) and 10.8g Vazo-67.After reactor content is heated to 120 ℃, the feed composition that maintains 115-125 ℃ was added continuously in the reactor in 5 hours.After interpolation is finished, mixture was left standstill 0.5-1 hour, then 5mmHg and 120 ℃ of following degassings 5 hours, to remove unreacted monomer and EB.Solids content: 40%; Viscosity: 6,000cps/25 ℃.
Embodiment 12-20: the polymerization of polymer polyatomic alcohol (POP 12-23)
Prepare polymer polyatomic alcohol in the mode identical with embodiment 11, except the kind of polyvalent alcohol (polyvalent alcohol C or D) and addition and ratio, the kind of dispersion stabilizer and the addition of amount and EB of addition, SM and AN change, as shown in following table 2.Component ratio in the table 2 is represented with ppw (weight part).
Comparative example 2 and 3
Prepare polymer polyatomic alcohol in the mode identical with embodiment 11, except the kind of polyvalent alcohol (polyvalent alcohol C and D) and addition and ratio, the amount of dispersion stabilizer and the addition of EB of amount, SM and AN change, as shown in table 2 below.The stablizer that uses comparative example 1 is as dispersion stabilizer.
Table 2: the embodiment 11-20 and comparative example 2 and 3 that are used for synthesis of polymer polyalcohol
| Embodiment | POP11 | POP12 | POP13 | POP14 | POP15 |
| Polyvalent alcohol | D | D | D | D | D |
| The addition of polyvalent alcohol | 57 | 57 | 57 | 57 | 57 |
| Dispersion stabilizer | SC 2 | SC 4 | SC 6 | SC 8 | SC 10 |
| The addition of dispersion stabilizer | 3 | 3 | 3 | 3 | 3 |
| The addition of SM | 20 | 20 | 20 | 20 | 20 |
| The addition of AN | 20 | 20 | 20 | 20 | 20 |
| Vazo-67 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| EB | 10 | 10 | 10 | 10 | 10 |
| Product characteristics | |||||
| Solids content (%) | 40.0 | 39.5 | 40.2 | 39.7 | 39.5 |
| Viscosity (cps/25 ℃) | 6,000 | 6,200 | 5,700 | 6,100 | 17,500 |
| Embodiment | POP16 | POP17 | POP18 | POP19 | POP20 | Comparative example 2 | Comparative example 3 |
| Polyvalent alcohol | C | C | C | C | C | D | C |
| The addition of polyvalent alcohol | 52 | 52 | 52 | 52 | 52 | 57 | 52 |
| Dispersion stabilizer | SC 2 | SC 4 | SC 6 | SC 8 | SC 10 | Comparative example 1 | Comparative example 1 |
| The addition of dispersion stabilizer | 5 | 5 | 5 | 5 | 5 | 3 | 5 |
| The addition of SM | 30 | 30 | 30 | 30 | 30 | 20 | 30 |
| The addition of AN | 13 | 13 | 13 | 13 | 13 | 20 | 13 |
| Vazo-67 | 0.55 | 0.55 | 0.55 | 0.55 | 0.55 | 0.4 | 0.55 |
| EB | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Product characteristics | |||||||
| Solids content (%) | 43.3 | 42.7 | 42.5 | 43.1 | 43.0 | 39.2 | 41.9 |
| Viscosity (cps/25 ℃) | 5,200 | 4,800 | 4,900 | 5,400 | 12,500 | 16,000 | 13,000 |
Embodiment 21-25: the preparation of urethane foam
Stir polymer polyatomic alcohol, polyvalent alcohol, silicone surfactant (L-580k), amine catalyst (A-1) and water, and the ratio shown in the following table 3 is mixed with each other, with the temperature regulation to 25 of mixture solution ℃.In mixture solution, add MC (methylene dichloride) and T-9 catalyzer, mixture was stirred for 10 seconds.Add T-80 then, mixture is 6, and 000rpm stirred for 6 seconds down, placed in the mould that is of a size of 20cm * 20cm * 20cm.After 15 minutes, the gained porous plastics is taken out from mould, after 24 hours, measure the mechanical property of porous plastics according to the method for ASTM D-3574.Measuring result is shown in the following table 4.
Comparative example 4
Prepare urethane foam in the mode identical, except using the polymer polyatomic alcohol of preparation in the comparative example 3 with embodiment 21-25.
Table 3
| Polymer polyatomic alcohol polyol E L-580k A-1 water | 50 50 1.7 0.11 5 |
| MC T-9 T-80 | 7.5 0.36 57.6 |
Table 4
| Test character | Test result | |||
| Embodiment 21 (POP 16) | Embodiment 22 (POP 17) | Embodiment 23 (POP 18) | ||
| Density hardness (25% compression) (60% compression) the elastic permanent compression strain of tearing strength hot strength percentage elongation | Kg/m 3 Kg/314cm 2 Kg/314cm 2 Kg/cm Kg/cm 2 ％ ％ ％ | 15.9 22.7 59.8 0.35 0.69 55.4 31 5.7 | 16.2 23.5 61.2 0.32 0.68 53.4 31 6.0 | 16.5 24.1 62.1 0.32 0.64 52.4 31 5.9 |
(continued)
| Test character | Test result | |||
| Embodiment 24 (POP 19) | Embodiment 25 (POP 20) | Comparative example 4 (comparative example 3) | ||
| Density hardness (25% compression) (60% compression) the elastic permanent compression strain of tearing strength hot strength percentage elongation | Kg/m 3 Kg/314cm 2 Kg/314cm 2 Kg/cm Kg/cm 2 ％ ％ ％ | 16.9 25.7 63.4 0.31 0.62 53.6 31 5.9 | 18.2 19.4 54.2 0.28 0.49 52 26 5.0 | 18.0 19.1 55.1 0.27 0.52 52.4 25 5.1 |
As mentioned above, the invention provides the dispersion stabilizer that is used to prepare polymer polyatomic alcohol, to have average functionality be that 4.5-8, molecular-weight average are 5 to described dispersion stabilizer by making, 000-15,000 and have the reaction of high sterically hindered polyvalent alcohol and vinyl trialkyl oxysilane and make, the present invention also provides the method for preparing this dispersion stabilizer at short notice with the cost efficient manner.In addition, in the polymer polyatomic alcohol preparation, use dispersion stabilizer to provide and have highly filled and low viscous polymer polyatomic alcohol.In addition, use polymer polyatomic alcohol that the physical properties of gained urethane foam is improved.
Claims (9)
1. dispersion stabilizer that is used to prepare polymer polyatomic alcohol, to have molecular-weight average be 5 to described dispersion stabilizer by making, 000-15,000 and average functionality be that polyether polyol and the vinyl trialkyl oxysilane reaction of 4.5-8 makes.
2. dispersion stabilizer as claimed in claim 1, wherein polyether polyol makes by polyhydroxy-alcohol in the mixture that makes the mixture, sorbyl alcohol and the sugar that select white sugar and glycerine and tetramethylolmethane and oxirane reaction.
3. dispersion stabilizer as claimed in claim 1, therein ethylene base trialkoxy silane is selected from: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane and their mixture.
4. the polymer polyatomic alcohol of preparation in the following way: in the presence of radical polymerization initiator, in containing the polyvalent alcohol that right requires 1 dispersion stabilizer, make one or more ethylenically unsaturated monomers polymerizations.
5. polymer polyatomic alcohol as claimed in claim 4, wherein radical polymerization initiator is an azo-compound.
6. polymer polyatomic alcohol as claimed in claim 4, wherein ethylbenzene is as chain-transfer agent.
7. polymer polyatomic alcohol as claimed in claim 4, wherein ethylenically unsaturated monomers is the mixture of vinylbenzene and vinyl cyanide.
8. polymer polyatomic alcohol as claimed in claim 7, wherein the ratio between vinylbenzene and the vinyl cyanide is 20: 80 to 80: 20.
9. method for preparing flexible polyurethane foam, described method comprises: in the presence of pore forming material and catalyzer, make among the claim 4-8 each polymer polyatomic alcohol and isocyanate compound reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040089544A KR100716220B1 (en) | 2004-11-05 | 2004-11-05 | Distribution stabilizer for the preparation of polymer polyol |
| KR1020040089544 | 2004-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1778829A true CN1778829A (en) | 2006-05-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005101202035A Pending CN1778829A (en) | 2004-11-05 | 2005-11-07 | Dispersion stabilizer made from vinyl trialkyl oxysilane and used for polymer popyalcohol preparation |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100716220B1 (en) |
| CN (1) | CN1778829A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532509A (en) * | 2010-12-20 | 2012-07-04 | 上海抚佳精细化工有限公司 | Preparation method for polymer polyol dispersion stabilizer |
| CN101687971B (en) * | 2007-07-11 | 2015-11-25 | 拜尔材料科学股份公司 | Process for preparing polyurethane foams based on specific alkoxysilane-functional polymers |
| CN108841000A (en) * | 2018-05-22 | 2018-11-20 | 龙口德源高分子科技有限公司 | A kind of synthetic method of vinyl dimethoxysilane blocking modification polyethers |
| CN112142942A (en) * | 2020-09-24 | 2020-12-29 | 南通馨宇诺家居用品有限公司 | Washable antibacterial mildew-proof memory foam and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19908562A1 (en) * | 1998-03-25 | 1999-10-07 | Henkel Kgaa | Polyurethane, used in e.g. adhesives |
-
2004
- 2004-11-05 KR KR1020040089544A patent/KR100716220B1/en active IP Right Grant
-
2005
- 2005-11-07 CN CNA2005101202035A patent/CN1778829A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687971B (en) * | 2007-07-11 | 2015-11-25 | 拜尔材料科学股份公司 | Process for preparing polyurethane foams based on specific alkoxysilane-functional polymers |
| CN102532509A (en) * | 2010-12-20 | 2012-07-04 | 上海抚佳精细化工有限公司 | Preparation method for polymer polyol dispersion stabilizer |
| CN102532509B (en) * | 2010-12-20 | 2014-03-05 | 上海抚佳精细化工有限公司 | Preparation method for polymer polyol dispersion stabilizer |
| CN108841000A (en) * | 2018-05-22 | 2018-11-20 | 龙口德源高分子科技有限公司 | A kind of synthetic method of vinyl dimethoxysilane blocking modification polyethers |
| CN112142942A (en) * | 2020-09-24 | 2020-12-29 | 南通馨宇诺家居用品有限公司 | Washable antibacterial mildew-proof memory foam and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060040264A (en) | 2006-05-10 |
| KR100716220B1 (en) | 2007-05-10 |
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