CN100509892C - Synthesis of grafted castor oil polyhydric alcohol polymer - Google Patents
Synthesis of grafted castor oil polyhydric alcohol polymer Download PDFInfo
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- CN100509892C CN100509892C CNB2007100405385A CN200710040538A CN100509892C CN 100509892 C CN100509892 C CN 100509892C CN B2007100405385 A CNB2007100405385 A CN B2007100405385A CN 200710040538 A CN200710040538 A CN 200710040538A CN 100509892 C CN100509892 C CN 100509892C
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- Prior art keywords
- polyhydric alcohol
- castor oil
- vinylbenzene
- grafted
- oil polyhydric
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Abstract
The invention discloses a method for synthesizing grafted castor oil polyhydric alcohol polymer, which comprises the following steps: adopting phenylethene and N-phenyl group maleimide (NPMI) as polymeric monomer; proceeding grafted polymerization reaction with the double bond of castor oil polyhydric alcohol; synthesizing the product. This invention adopts castor oil polyhydric alcohol with low price as raw material, which craft is simpler.
Description
Technical field:
The present invention relates to the synthetic method of grafted castor oil polyhydric alcohol polymer.
Background technology:
Derived product propylene oxide, glycerine of oil etc., resource anxiety and cost height are mainly used in the production of present existing polyether glycol.In recent years, both at home and abroad part company makes full use of some cheap vegetables oil such as soybean oil, plam oil is a raw material, develops a series of vegetable oil polyols (as castor oil polyhydric alcohol) and substitutes conventional polyether glycol.At the 10--15 in future, the various constituent materialss of the alternative petroleum refining of vegetable oil-based polyols are used to make polyurethane foam, elastomerics, coating, tackiness agent and sealing agent etc.
Constantly perfect along with environmental regulation, people are also more and more higher to the requirement of the flame retardant properties of material, and using additive flame retardant is the most frequently used method.But in the exigent field of flame retardant properties, additive flame retardant is difficult to reach service requirements, and this is because there is easily migration in additive flame retardant, can not keeps shortcomings such as flame retardant effect and destruction foam physics performance lastingly.The appearance of fire resistant polymer polylol just can ideally address the above problem.At present, the system that synthesis of polymer polyalcohol adopted generally is a polyether glycol, does not adopt castor oil polyhydric alcohol as reaction system.The synthetic monomer is vinyl cyanide, vinylbenzene, α-vinyl toluene, acrylate, acrylamide and derivative thereof etc. normally.But residual acrylonitrile monemer severe toxicity in the system of reaction back, and vinyl cyanide itself has flame-retarding characteristic not as N-phenylmaleimide (NPMI).
Summary of the invention
At the defective of prior art, the invention provides a kind of method of grafted castor oil polyhydric alcohol.It is polymerization single polymerization monomer that the present invention adopts vinylbenzene and N-phenylmaleimide (NPMI), with the two key generation graft polymerization reactions in the castor oil polyhydric alcohol, has synthesized grafted castor oil polyhydric alcohol polymer.But the monomeric step of synthetic macromolecule does not make technology simpler in order to introduce the reaction double key in system when not containing residual severe toxicity third rare nitrile monomer in the system and having exempted with polyether glycol.
Realize that technical scheme of the present invention is as follows:
A kind of synthetic method of grafted castor oil polyhydric alcohol, it is characterized in that, commercially available castor oil polyhydric alcohol was dewatered 1 hour under vacuum, charge into protection of inert gas, can add viscosity-depression agent and dispersion agent when needing, behind the logical water of condensation, with the Diisopropyl azodicarboxylate is initiator, dropwise add vinylbenzene and pyridyl maleimide and chain-transfer agent while stirring respectively, the tear drop temperature is 50 ℃-120 ℃, and the tear drop reaction times is 1-5 hour; After tear drop is finished, under 50 ℃-120 ℃, continue reaction 10-150 minute, obtain the synthetic product grafted castor oil polyhydric alcohol after removing unreacted monomer or viscosity-depression agent.
Wherein, the monomeric charge of vinylbenzene/pyridyl maleimide is than being 100-20wt%, and total charging capacity of vinylbenzene and pyridyl maleimide accounts for the 1-70wt% of reaction system total amount,
Chain-transfer agent is alkyl sulfhydryl or Virahol, and its consumption is the 0-40wt% of vinylbenzene and the total consumption of pyridyl maleimide monomer,
The consumption of initiator Diisopropyl azodicarboxylate is the 0.05-5wt% of vinylbenzene and the total consumption of pyridyl maleimide monomer.
Viscosity-depression agent is glycol dimethyl ether or ethylene glycol diethyl ether or ethyl acetate, and its consumption accounts for the 0-30wt% of reaction system total amount,
Dispersion agent is commercially available OP series or tween series, and consumption is the 0-35wt% of vinylbenzene and the total consumption of pyridyl maleimide monomer.
Among the present invention, copolymerization takes place in vinylbenzene and pyridyl maleimide in the system that with the castor oil polyhydric alcohol is medium, and utilize the two keys on the castor oil polyhydric alcohol to make partial monosomy or its copolymerization product and castor oil polyhydric alcohol generation graft polymerization, generate grafted castor oil polyhydric alcohol polymer.Whole system is grafted castor oil polyhydric alcohol, the common stable dispersion system that exists of grafted castor oil polyhydric alcohol, styrene homopolymers, vinylbenzene and pyridyl maleimide copolymer and small amount of nitrogen phenyl maleimide homopolymer not.Its reaction mechanism is as follows:
The molecular weight of synthetic product is: 1000-35000.
Synthetic product can be used for and mechanical property, solvent resistance and the thermal property of isocyanate reaction synthesis of polyurethane material with the raising polyurethane material.
Beneficial effect
Compared with prior art, the present invention has the following advantages:
1, to have adopted the lower castor oil polyhydric alcohol of price be raw material in the present invention, can be used as the raw material of polyurethane material, gives certain flame-retarding characteristic of synthetic polyurethane material and mechanical property.
2, do not introduce itrile group, haloid element in the system, but introduced N-phenylmaleimide as fire-retardant monomer, utilize vinylbenzene and N-phenylmaleimide (NPMI) copolyreaction and with the home position polymerization reaction of castor oil polyhydric alcohol, synthesized a kind of novel grafted castor oil polyhydric alcohol, can not emit obnoxious flavour during burning, more friendly to environment.
3, saved the monomeric processing step of synthetic macromolecule
Below by embodiment the present invention is further elaborated
Embodiment one:
With 190 gram hydroxyl values is that 165 castor oil polyhydric alcohol input is equipped with in thermometer and the churned mechanically four-hole boiling flask, and dehydration is 1 hour about 105 ℃.Four-hole boiling flask is led to argon shield and connects the condensing reflux pipe; behind the temperature control to 80 ℃; 13.83 gram glycol dimethyl ethers (viscosity-depression agent) and 4.2 gram Virahols are put in the four-hole boiling flask; then under high-speed stirring; beginning drips vinylbenzene 63 grams that are dissolved with 1.26 gram AIBN (ethyl alcohol recrystallization is exquisite to be crossed) simultaneously in system; with 15 gram nitrogen-phenyl maleimides, the dropping time was controlled at about 140 minutes, and system is warming up to and continues reaction 25 minutes about 90 ℃ after dropwising.After reaction finished, decompression removed viscosity-depression agent glycol dimethyl ether and unreacted monomer near 100 ℃, obtained solid content and be the dispersion liquid of 30% the milk yellow that viscosity is less, particle is thicker, was the synthetic product grafted castor oil polyhydric alcohol.
The oxygen index of the polyurethane foam that makes with this synthetic product is 23.Elastomeric hardness is 60A
Embodiment two:
With 190 gram hydroxyl values is that 165 castor oil polyhydric alcohol and 0.9 gram OP-40 (dispersion agent) drop into and be equipped with in thermometer and the churned mechanically four-hole boiling flask, and dehydration is 1 hour about 105 ℃.Four-hole boiling flask is led to argon shield and connects the condensing reflux pipe; behind the temperature control to 98 ℃; beginning drips vinylbenzene 75 grams that are dissolved with 1.8 gram AIBN and 1.8 gram lauryl mercaptans simultaneously in system under high-speed stirring; with 15 gram nitrogen-phenyl maleimides; the dropping time was controlled at about 180 minutes, and system is warming up to and continues reaction 60 minutes about 115 ℃ after dropwising.After reaction finished, decompression removed unreacted monomer near 100 ℃, can obtain solid content and be the dispersion liquid of 31.6% the milk yellow that viscosity is big, particle is thinner, was the synthetic product grafted castor oil polyhydric alcohol.
The oxygen index of the polyurethane foam that makes with this synthetic product is 23.5.Elastomeric hardness is 65A
Claims (2)
1, a kind of synthetic method of grafted castor oil polyhydric alcohol, it is characterized in that, commercially available castor oil polyhydric alcohol was dewatered 1 hour under vacuum, charge into protection of inert gas, behind the logical water of condensation, be initiator, dropwise add vinylbenzene and pyridyl maleimide and chain-transfer agent while stirring respectively with the Diisopropyl azodicarboxylate, the tear drop temperature is 50 ℃-120 ℃, and the tear drop reaction times is 1-5 hour; After tear drop is finished, under 50 ℃-120 ℃, continue reaction 10-150 minute, obtain the synthetic product grafted castor oil polyhydric alcohol after removing unreacted monomer.
Wherein, the monomeric charge of vinylbenzene/pyridyl maleimide is than being 100-20wt%, and total charging capacity of vinylbenzene and pyridyl maleimide accounts for the 1-70wt% of reaction system total amount,
Chain-transfer agent is alkyl sulfhydryl or Virahol, and its consumption is the 0-40wt% of vinylbenzene and the total consumption of pyridyl maleimide monomer,
The consumption of initiator Diisopropyl azodicarboxylate is the 0.05-5wt% of vinylbenzene and the total consumption of pyridyl maleimide monomer,
2, the synthetic method of grafted castor oil polyhydric alcohol as claimed in claim 1 is characterized in that, after charging into rare gas element, adds viscosity-depression agent and dispersion agent;
Wherein, viscosity-depression agent is glycol dimethyl ether or ethylene glycol diethyl ether or ethyl acetate, and its consumption accounts for the 0-30wt% of reaction system total amount,
Dispersion agent is commercially available OP series or tween series, and its consumption is the 0-35wt% of vinylbenzene and the total consumption of pyridyl maleimide monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100405385A CN100509892C (en) | 2007-05-11 | 2007-05-11 | Synthesis of grafted castor oil polyhydric alcohol polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100405385A CN100509892C (en) | 2007-05-11 | 2007-05-11 | Synthesis of grafted castor oil polyhydric alcohol polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101062968A CN101062968A (en) | 2007-10-31 |
| CN100509892C true CN100509892C (en) | 2009-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2007100405385A Expired - Fee Related CN100509892C (en) | 2007-05-11 | 2007-05-11 | Synthesis of grafted castor oil polyhydric alcohol polymer |
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| Country | Link |
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| CN (1) | CN100509892C (en) |
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2007
- 2007-05-11 CN CNB2007100405385A patent/CN100509892C/en not_active Expired - Fee Related
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| CN101062968A (en) | 2007-10-31 |
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Granted publication date: 20090708 Termination date: 20120511 |