CN100491428C - Process for synthesis of polymer polyhydric alcohol - Google Patents
Process for synthesis of polymer polyhydric alcohol Download PDFInfo
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- CN100491428C CN100491428C CNB2006101023006A CN200610102300A CN100491428C CN 100491428 C CN100491428 C CN 100491428C CN B2006101023006 A CNB2006101023006 A CN B2006101023006A CN 200610102300 A CN200610102300 A CN 200610102300A CN 100491428 C CN100491428 C CN 100491428C
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Abstract
The invention relates to a method for preparing polymer polyatomic alcohol, comprising following steps: putting vegetable oil and polyatomic alcohol into reactor, adding fused isocyanate after vacuum dehydration, gettign macromolecule polymer after reaction; mixing macromolecule polymer and basic polyester polyol or basic polyether polyol evenly, dropping mixed polymerizing monomer and initiating agent into said mixture, getting polymer polyatomic alcohol through compression after polymerization at original position. The invention is characterized by easy process, convenient operation, low viscosity of polymer polyatomic alcohol,, good stability and low price.
Description
Technical field
The present invention relates to a kind of method for preparing polymer polyatomic alcohol, relate in particular to a kind of method that contains vegetables oil segmental performed polymer used as stabilizers synthesis of polymer polyalcohol by use.
Technical background
Polymer polyatomic alcohol is usually used in making various polyurethane foams.Polyurethane foam is widely used in the every field.Main field is automobile and airplane industry, furniture and mechanicals and sole material etc.For example, full porous plastics, the upper strata pad at seat.Carpet lining, base wad and mattress.Packing ring between automobile body and the monomer, the width of cloth that is used for the air filtration body of engine reduces the insulation layer of noise and vibrations on sealing member and trolley part and engine parts.Should understand various concrete application used foam is had specific requirement.Key character is a foamy hardness in this respect, density, elasticity and decay behavior.And for various application cooperate, these features should be carried out optimum balance and adjusting.Polymer polyatomic alcohol can effectively improve the foamy percentage of open area and its mechanical property is improved along with the raising of hardness.This reduces density when just making polyurethane foam keep equal mechanical property, thereby reduces cost.Has wide prospect in industrial application.
In the macromole stablizer of polyether polymer polyvalent alcohol synthetic, U.S.Pat.No.4 synthesizes the macromole that contains unsaturated double-bond with undersaturated acid or acid anhydrides in 625,589.U.S.Pat.No.4, in 625,589 with the synthetic macromole that contains unsaturated double-bond of undersaturated isocyanic ester.U.S.Pat.No.4, in 357,430 with not only containing two keys but also contain the synthetic performed polymer of combination polyvalent alcohol of propylene oxide, thereby improve the stability of product.To cause the viscosity of product too big but these methods are used for the polyester polymers polyvalent alcohol, and can not solve the problem of stability.ES 557 716, ES 555 890 and EP-A 250 351 all mention with undersaturated polyester and make the base polyester synthesis of polymer polyalcohol, though products obtained therefrom is stable, but in building-up process, unavoidably bring crosslinked generation, thereby make product viscosity excessive, can not satisfy industrial requirement.U.S.Pat.No.5 synthesizes performed polymer with saturated polyester and isocyanic ester in 830,944, U.S.Pat.No.6, the polyester that 433,031 usefulness contain mercaptan all can obtain the lower polyester type polymer polyatomic alcohol of viscosity, but the poor stability of its product is easy to generate layering.
Summary of the invention
The object of the invention provides a kind of synthetic method of polymer polyatomic alcohol of good stability, contains the method that vegetables oil segmental performed polymer used as stabilizers carries out synthesis of polymer polyalcohol by use.
Method of the present invention is divided into two step of reaction: stablizer macromole synthesis phase and polymer polyatomic alcohol synthesis phase.
(1) at the macromole synthesis phase
Be 1:0～100 by the mass ratio of vegetables oil and polyvalent alcohol earlier,, vacuumize temperature and rise to 100 ℃～120 ℃ and vacuumize the 1h～3h that dewaters preferably than be in 1:0～10 adding reactors with vegetables oil and polyvalent alcohol; System is cooled to 80 ℃, obtain vegetables oil and polyol blends, by in vegetables oil and the polyvalent alcohol-mol ratio of the NCO of OH sum and isocyanic ester is 1:0.5～2, be preferably 1:0.5～1.5, be preferably 1:0.5～1 especially and add the fused isocyanic ester at vegetables oil and polyol blends, reaction times is 1h～24h, is preferably 2h～4h; Temperature of reaction is 80 ℃～150 ℃, preferred 80 ℃～130 ℃, obtains high polymer;
(2) polymer polyatomic alcohol synthesis phase
At first high polymer and base polyester polyvalent alcohol or basic polyether glycol are mixed, then with the polymerization single polymerization monomer that mixes and initiator under 80 ℃～150 ℃, be added drop-wise in the mixture of macromole and base polyester polyvalent alcohol or basic polyether glycol, the temperature of home position polymerization reaction is 80 ℃～150 ℃, optimal selection is 100 ℃～140 ℃, the time of reaction is 0.5h～10h, is preferably 0.5h～5h, and optimum is 1h～4h.Reduce pressure after reacting completely polymer polyatomic alcohol;
The high polymer consumption accounts for 0.5%～30% of all polymer polyatomic alcohol total mass per-cents, and optimum quality per-cent is 1%～10%; The polymerization single polymerization monomer consumption accounts for 10%～90% of all polymer polyatomic alcohol total mass per-cents, and optimum quality per-cent is 10%～40%; Initiator amount accounts for 0.01%～20% of polymerization single polymerization monomer total amount, and wherein the optimum quality ratio is 0.1%～10%; Base polyester polyvalent alcohol or basic polyether glycol consumption account for 10%～90% of all polymer polyatomic alcohol total mass per-cents, and optimum quality per-cent is 40%～60%.
Aforesaid vegetables oil is Viscotrol C or soybean oil, is preferably Viscotrol C.
Aforesaid isocyanic ester can be selected tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), carbodiimide modification MDI (C-MDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), PPDI (PPDI); Be preferably tolylene diisocyanate (TDI) or diphenylmethanediisocyanate (MDI).
The base polyester polyvalent alcohol is 450mPas～1200mPas 75 ℃ viscosity usually, and molecular weight is generally 1000～8000.
The basis polyether glycol is 450mPas～800mPas 75 ℃ viscosity usually, and molecular weight is generally 5000～8000.The basis polyether glycol can be selected polyoxytrimethylene ethoxylated polyhydric alcohol (PPG) and polytetrahydrofuran polyvalent alcohol (PTMG), preferred polyoxytrimethylene ethoxylated polyhydric alcohol (PPG).
Polymerization single polymerization monomer can be selected vinylbenzene or vinylbenzene and contain the monomeric mixture of Shuan Key.The monomer that contains Shuan Key can select vinyl cyanide, maleic anhydride, methyl acrylate, ethyl propenoate, vinyl acetate, methyl methacrylate, Jia Jibingxisuanyizhi or vinylidene chloride.The optimum mixture that is chosen as vinylbenzene and vinyl cyanide.In mix monomer, cinnamic consumption accounts for 10%～90% of all polymerization single polymerization monomer weight, and optimum is 40%～80%.
Initiator is for the material of initiation free radical reaction commonly used etc., as: Diisopropyl azodicarboxylate, dicumyl peroxide, dibenzoyl peroxide, the peroxy dicarbonate ethylhexyl, t-butyl hydrogen peroxide, special butyl ester of benzoyl peroxide or di-isopropyl peroxydicarbonate etc.; Be preferably Diisopropyl azodicarboxylate or dicumyl peroxide.
The product of the present invention's preparation is stable, is uniformly dispersed, and low viscous white liquid, its viscosity is lower than 6000mPas in the time of 75 ℃, is used for foaming and can increases substantially the foamy mechanical property.
The present invention has following advantage compared with the prior art:
Selected vegetables oil can increase substantially the utilization of renewable resources, reduces the dependence of present product to petroleum resources, and to the pollution of environment.And vegetables oil is cheap, can effectively reduce raw materials cost.
Wherein the technology of synthetic polymer macromole and polymer polyatomic alcohol is simple, is convenient to operation.
The polymer polyatomic alcohol viscosity of gained is low, good stability, low price.
Embodiment
Embodiment 1
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system, add the 60g Viscotrol C, the PPG of 90g molecular weight 3000,110 ℃ of following vacuum hydro-extraction 1h.When system is cooled to 80 ℃, under stirring fast, slowly add 10g MDI, 80 ℃～90 ℃ are reacted 3h down.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system and inlet system, adding the 100g molecular weight is 5000, the macromonomer that the PPG of three-functionality-degree and 7.5g reaction generate.When reaction vessel is warming up to 110 ℃, under quick stirring condition, 40g vinylbenzene, the mixture of 10g vinyl cyanide and 1.0g Diisopropyl azodicarboxylate slowly is added dropwise in the reactor, and the dropping time is 2h, and temperature remains at 110 ℃ in the dropping process.Dropwise afterreaction under 105 ℃～110 ℃ conditions, continue reaction 3h. and reduce to minimum for the monomer that makes reaction is remaining, system vacuumizes 1h. under 120 ℃
The polyether type polymer system hydroxyl value of gained is a 25mg KOH gram equivalent, and acid number is a 0.45mg KOH gram equivalent, and water-content is 0.01wt%, and its viscosity is 1300mPas in the time of 75 ℃, and the remaining content of vinylbenzene is 0.01wt%.
Embodiment 2
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system, add 110 ℃ of following vacuum hydro-extraction 1h of 60g Viscotrol C.When system is cooled to 80 ℃, under stirring fast, slowly add 10g MDI, 80 ℃～90 ℃ are reacted 4h down.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system and inlet system, the 100g molecular weight is 2000, the macromonomer that the PPG of three-functionality-degree and 4g reaction generate.When reaction vessel is warming up to 130 ℃, under quick stirring condition, 45g vinylbenzene, the mixture of 5g vinyl cyanide and 1.0g peroxide diisopropylbenzene(DIPB) slowly is added dropwise in the reactor, and the dropping time is 2h, and temperature remains at 130 ℃ in the dropping process.Dropwise afterreaction under 125 ℃～130 ℃ conditions, continue reaction 3h.Reduce to minimum for the monomer that makes reaction is remaining, system vacuumizes 1h under 120 ℃.
The polyether type polymer polyvalent alcohol system hydroxyl value of gained is a 55mg KOH gram equivalent, and acid number is a 0.37mg KOH gram equivalent, and water-content is 0.02wt%, and its viscosity is 1200mPas in the time of 75 ℃, and the remaining content of vinylbenzene is 0.015wt%.
Embodiment 3
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system, add the 60g Viscotrol C, the polyester polyol of the hexanodioic acid of 90g molecular weight 1500 and ethylene glycol polycondensation, 110 ℃ of following vacuum hydro-extraction 1h.When system is cooled to 80 ℃, under stirring fast, slowly add 10g MDI, 130 ℃～140 ℃ are reacted 2h down.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system and inlet system, adding the 100g molecular weight is 1500, the macromonomer that is generated by hexanodioic acid and ethylene glycol synthetic polyester and 10g reaction.When reaction vessel was warming up to 130 ℃, under quick stirring condition, the mixture of 40g vinylbenzene and 5g vinyl cyanide and 1.0g Diisopropyl azodicarboxylate slowly was added dropwise in the reactor, and the dropping time is 2h, and temperature remains at 140 ℃ in the dropping process.Dropwise afterreaction under 135 ℃～140 ℃ conditions, continue reaction 1h. and reduce to minimum for the monomer that makes reaction is remaining, system vacuumizes 1h. under 120 ℃
The polyester type polymer polyatomic alcohol system hydroxyl value of gained is a 74mg KOH gram equivalent, and acid number is a 0.3mg KOH gram equivalent, and water-content is 0.01wt%, and its viscosity is 2000mPas in the time of 75 ℃, and the remaining content of vinylbenzene is 0.01wt%.
Embodiment 4
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system, add 110 ℃ of following vacuum hydro-extraction 1h of 60g Viscotrol C.When system is cooled to 80 ℃, under stirring fast, slowly add 5g MDI, 120 ℃～130 ℃ are reacted 4h down.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system and inlet system, adding the 100g molecular weight is 1500, the macromonomer that is generated by pentanedioic acid and propylene glycol synthetic polyester and 8.5g reaction.When reaction vessel was warming up to 130 ℃, under quick stirring condition, the mixture of 45g vinylbenzene and 1.0g azo-bis-isobutyl cyanide slowly was added dropwise in the reactor, and the dropping time is 2h, and temperature remains at 130 ℃ in the dropping process.Dropwise afterreaction under 125 ℃～130 ℃ conditions, continue reaction 3h. and reduce to minimum for the monomer that makes reaction is remaining, system vacuumizes 1h. under 120 ℃
The polyester type of gained gathers and thing polyvalent alcohol system hydroxyl value is a 69mg KOH gram equivalent, and acid number is a 0.3mg KOH gram equivalent, and water-content is 0.01wt%, and its viscosity is 2700mPas in the time of 75 ℃, and the remaining content of vinylbenzene is 0.02wt%.
Embodiment 5
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system, add 110 ℃ of following vacuum hydro-extraction 1h of 60g Viscotrol C.When system is cooled to 80 ℃, under stirring fast, slowly add 5g MDI, 100 ℃～110 ℃ are reacted 3h down.
In a reaction vessel of being furnished with heated and stirred system, temp measuring system and condenser system and inlet system, adding the 100g molecular weight is 1500, the macromonomer that is generated by pentanedioic acid and propylene glycol synthetic polyester and 8.5g reaction.When reaction vessel is warming up to 130 ℃, under quick stirring condition, 45g vinylbenzene, the mixture of 5g vinyl cyanide and 3.0g dicumyl peroxide slowly is added dropwise in the reactor, and the dropping time is 2h, and temperature remains at 130 ℃ in the dropping process.Dropwise afterreaction under 125 ℃～130 ℃ conditions, continue reaction 3h. and reduce to minimum for the monomer that makes reaction is remaining, system vacuumizes 1h. under 120 ℃
The polyether-type of gained gathers and thing polyvalent alcohol system hydroxyl value is a 71mg KOH gram equivalent, and acid number is a 0.45mg KOH gram equivalent, and water-content is 0.01wt%, and its viscosity is 3500mPas in the time of 75 ℃, and the remaining content of vinylbenzene is 0.02wt%.
Claims (16)
1, a kind of method of synthesis of polymer polyalcohol is characterized in that comprising the steps:
(1) macromole synthesis phase
Be 1:0～1.5 by the mass ratio of vegetables oil and base polyester polyvalent alcohol or basic polyether glycol earlier, add in the reactor, vacuumize temperature and rise to 100 ℃～120 ℃ and vacuumize the 1h～3h that dewaters vegetables oil and base polyester polyvalent alcohol or basic polyether glycol; System is cooled to 80 ℃, obtain vegetables oil and polyol blends, by in vegetables oil and the polyvalent alcohol-mol ratio of the NCO of OH sum and isocyanic ester is that 1:0.5～2 add the fused isocyanic ester at vegetables oil and polyol blends, reaction times is 1h～24h, temperature of reaction is 80 ℃～150 ℃, obtains high polymer;
(2) polymer polyatomic alcohol synthesis phase
At first high polymer and base polyester polyvalent alcohol or basic polyether glycol are mixed, then with the polymerization single polymerization monomer that mixes and initiator under 80 ℃～150 ℃, be added drop-wise in the mixture of macromole and base polyester polyvalent alcohol or basic polyether glycol, the temperature of home position polymerization reaction is 80 ℃～150 ℃, the reaction time be 0.5h～10h, reduce pressure after reacting completely polymer polyatomic alcohol;
It is 0.5%～30% that the high polymer consumption accounts for all polymer polyatomic alcohol total mass per-cents; It is 10%～90% that the polymerization single polymerization monomer consumption accounts for all polymer polyatomic alcohol total mass per-cents; It is 0.01%～20% that initiator amount accounts for polymerization single polymerization monomer total mass per-cent; It is 10%～90% that base polyester polyvalent alcohol or basic polyether glycol consumption account for all polymer polyatomic alcohol total mass per-cents;
Described polymerization single polymerization monomer is vinylbenzene or vinylbenzene and the monomeric mixture that contains Shuan Key, and in mix monomer, cinnamic consumption accounts for 10%～90% of all polymerization single polymerization monomer weight;
The monomer of the described Shuan of containing Key is vinyl cyanide, maleic anhydride, methyl acrylate, ethyl propenoate, vinyl acetate, methyl methacrylate, Jia Jibingxisuanyizhi or vinylidene chloride.
2, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1 is characterized in that described vegetables oil is Viscotrol C or soybean oil.
3, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 2 is characterized in that described vegetables oil is a Viscotrol C.
4, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1, it is characterized in that described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, carbodiimide modification MDI, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate or PPDI.
5, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 4 is characterized in that described isocyanic ester is tolylene diisocyanate or diphenylmethanediisocyanate.
6, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1 is characterized in that described base polyester polyvalent alcohol is 450mPas～1200mPas 75 ℃ viscosity, and molecular weight is 1000～8000.
7, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1 is characterized in that described basic polyether glycol is 450mPas～800mPas 75 ℃ viscosity, and molecular weight is 5000～8000.
8, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1 is characterized in that described basic polyether glycol is polyoxytrimethylene ethoxylated polyhydric alcohol or polytetrahydrofuran polyvalent alcohol.
9, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1 is characterized in that described basic polyether glycol is the polyoxytrimethylene ethoxylated polyhydric alcohol.
10, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1 is characterized in that in the described mix monomer, cinnamic consumption accounts for 40%～80% of all polymerization single polymerization monomer weight.
11, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1, it is characterized in that described initiator is a Diisopropyl azodicarboxylate, dicumyl peroxide, dibenzoyl peroxide, the peroxy dicarbonate ethylhexyl, t-butyl hydrogen peroxide, special butyl ester of benzoyl peroxide or di-isopropyl peroxydicarbonate.
12, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 11 is characterized in that described initiator is Diisopropyl azodicarboxylate or dicumyl peroxide.
13, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1, it is characterized in that described in (1) step in vegetables oil and the polyvalent alcohol-mol ratio of the NCO of OH sum and isocyanic ester is 1:0.5～1.5, the reaction times is 2h～4h; Temperature of reaction is 80 ℃～130 ℃.
14, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 13, it is characterized in that in described vegetables oil and the polyvalent alcohol-mol ratio of the NCO of OH sum and isocyanic ester is 1:0.5～1.
15, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 1, the temperature that it is characterized in that described (2) step home position polymerization reaction are 100 ℃～140 ℃, the time 0.5h～5h of reaction; It is 1%～10% that the high polymer consumption accounts for all polymer polyatomic alcohol total mass per-cents; It is 10%～40% that the polymerization single polymerization monomer consumption accounts for all polymer polyatomic alcohol total mass per-cents; It is 0.1%～10% that initiator amount accounts for polymerization single polymerization monomer total mass per-cent; It is 40%～60% that base polyester polyvalent alcohol or basic polyether glycol consumption account for all polymer polyatomic alcohol total mass per-cents.
16, the method for a kind of synthesis of polymer polyalcohol as claimed in claim 15, the time that it is characterized in that described (2) step home position polymerization reaction is 1h～4h.
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Families Citing this family (5)
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| CN101343347B (en) * | 2008-09-02 | 2011-09-21 | 北京市丰信德科技发展有限公司 | Method for synthesis of high solid content polymer polyol macromer with vegetable oil and uses thereof |
| JP2014530265A (en) | 2011-09-12 | 2014-11-17 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Graft polyol and method for forming the same |
| CN103145923B (en) * | 2013-01-31 | 2015-05-06 | 北京化工大学常州先进材料研究院 | Preparation method of polymerizable oligomer based on soybean oil route |
| CN108164677A (en) * | 2018-01-23 | 2018-06-15 | 广州市聚科聚氨酯有限公司 | Soybean oil polyol prepares and its application in polyurethane foam |
| CN113980219B (en) * | 2021-10-22 | 2023-01-17 | 东莞市米儿塑胶原料有限公司 | Preparation method of semitransparent antistatic TPU master batch |
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| US4390645A (en) * | 1979-11-23 | 1983-06-28 | The Dow Chemical Company | Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom |
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Assignee: Zibo Dexin Lianbang Chemical Industry Co., Ltd. Assignor: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Contract record no.: 2010370000446 Denomination of invention: Process for synthesis of polymer polyhydric alcohol Granted publication date: 20090527 License type: Exclusive License Open date: 20070801 Record date: 20100810 |
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