CN1042542C - High performance formol polymerization retarder and preparing process thereof - Google Patents
High performance formol polymerization retarder and preparing process thereof Download PDFInfo
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- CN1042542C CN1042542C CN94109260A CN94109260A CN1042542C CN 1042542 C CN1042542 C CN 1042542C CN 94109260 A CN94109260 A CN 94109260A CN 94109260 A CN94109260 A CN 94109260A CN 1042542 C CN1042542 C CN 1042542C
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- polymerization
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- vinyl acetate
- formol
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Abstract
The present invention relates to a high performance formol polymerization retarder and a preparing method thereof, which belongs to the technical field of a homopolymer having one or more unsaturated aliphatic group compounds. The viscosity-average molecular weight is from 1000 to 17000, and the content of acetyl is from 20% to 60%. A great amount of initiating agent (AIBN) is used in a VAC polymerization process. Compressing air is utilized to recover solvent methanol. The dosage of catalyst concentrated sulfuric acid is 8.5 to 9.5%(Wt) of the dosage of the PVAC in an acetalation reaction process. The product has the advantages of low viscosity-average molecular weight, concentrated distribution, good solubility and high conversion rate. The solution can not be foamed, which enhances the polymerization retarding performance. The formol polymerization retarder can be utilized in severe cold.
Description
The invention belongs to homopolymer technical field, be specifically related to the preparation method of a kind of high performance formol polymerization retarder (polyvinylacetal) with one or more unsaturated aliphatic based compounds.
Known to the applicant, the prior art relevant with the present invention arranged, as " commercial process of formaldehyde anti-polymerization agent " (CN 1053615A).The method production formol polymerization retarder of announcing with CN 1053615A is the comparison success, but also has following defective: the dissolution time of product long (about a day), also need heat sometimes; Solubleness is low, also has insolubles sometimes; After particularly adding the industrial formol aqueous solution about 37%, formaldehyde can foaming in transportation, makes eight tons the tank car of can packing into originally can only adorn five to six tons, can not make full use of container containing; Under the very low environment of temperature, add a certain amount of stopper, formaldehyde solution still can polymerization, can not satisfy that severe cold area is stored and the needs of transportation.
Purpose of the present invention be exactly to provide a kind of can produce solvability good, add the preparation method that back formaldehyde solution can not foam, be suitable for the high performance formol polymerization retarder that uses under the various envrionment temperatures.
High performance formol polymerization retarder of the present invention, its structural formula is:
Abc is a natural number in the formula, in hydroformylation thing molecule,
The content of vinyl acetal base is 25-75% (Wt);
The content of vinyl, ethanoyl is 20-60% (Wt);
Other is the ethene alcohol radical.
The viscosity-average molecular weight of product of the present invention (in vinyl acetate between to for plastic) is low, is 10000-17000.
Technical process of the present invention comprises the following steps:
The polymerization of vinyl acetate between to for plastic (VAC), solvent recuperation (being directly used in polymerization after the recovery), acetalation, in and moulding, washing, centrifuge dripping, drying and finished product packing.
Below each operation is explained (percentage ratio of following use is weight percentage):
In the VAC polymerization technique, adopt the initiator Diisopropyl azodicarboxylate (AIBN) of super large dosage, its consumption is 0.1～0.15% of vinyl acetate between to for plastic (VAC) consumption.In polymerization technology, use the high dense methanol solvate of 75-80%; Polymeric reaction temperature is 55-60 ℃; Reclaim solvent methanol with pressurized air; In acetalation technology, the consumption of the catalyzer vitriol oil is the 8.5-9.5% of PVAC; In and moulding process in two header tanks are arranged.
The present invention adds material enamel reaction still or accordingly in other reactors, the AIBN methanol solution is housed in the reactor, heats to 55-60 ℃ backflow polymerization 13-14 hour.For accurate control reaction temperature, contriver's specialized designs heating curve, heat by this curve.The present invention adopts super amount initiator A IBN, its consumption is 10-15 a times of industrial preparation PVAC initiator amount, its purpose is to provide condition for the down synthetic PVAC of lesser temps, low to obtain viscosity-average molecular weight, the poly-good stopper of property of resistance, and improve transformation efficiency, reach about 80%, facts have proved that viscosity-average molecular weight is low more, solvability is good more.
The present invention uses the high dense methanol solvate of 75-80%, and its reason is that methyl alcohol is solvent, is again a kind of chain-transfer agent, can utilize its chain transfer function to regulate the molecular weight of PVAC, and the concentration of methyl alcohol is big more, and the molecular weight of PVAC is low more.So, adopt the methanol solvate concentration of 60-70 to compare the low product of the easier acquisition viscosity-average molecular weight of the present invention with prior art.
It is 55-60 ℃ that the present invention adopts polymerization temperature.Its reason is: polymerization at a lower temperature can obtain all better polymerization things (PVAC) of systematicness and quality, and improve percent polymerization; Because temperature of reaction descends than oligomerization speed, so prolonged polymerization time and strengthened initiator amount.
The present invention reclaims solvent methanol with pressurized air.The pressurized air of pressure 〉=0.2MPa is fed in the reactor, and recovery part methanol solvate and unreacted VAC can be directly used in next polymerization.Since when reclaiming methyl alcohol along with its content reduces gradually, can cause the fluctuation of PVAC molecular weight, and the oxygen in the pressurized air has inhibition to the polymerization of VAC, thereby suppresses the fluctuation of its molecular weight, so the present invention changes compressed nitrogen of the prior art into pressurized air.
Among the present invention, the catalyst levels of employing is 3-4 a times of prior art, and purpose is that an acetal base is controlled in the preferred range, to improve the polymerization inhibition performance of product.
The present invention is owing to set up second header tank, and reaction solution becomes thinner thread back by pore and flows in the Potassium ethanoate aqueous solution, and product is easier separates out.
The present invention compared with prior art has following outstanding advantage:
Preparation method of the present invention, owing to adopted above-mentioned processing condition and the measure that is different from prior art, breakthrough progress has been arranged, the viscosity-average molecular weight of product is low and distribute concentrated, not only solvability is good, transformation efficiency is high, more importantly be that solution can not foam after adding formaldehyde solution, improved the poly-property of resistance widely, can under the temperature condition of severe cold, use.Through entrust test center's test proofs such as Shanghai Wu Jing chemical general factory, Jiamusi evolution factory, Yunnan nitrogen fertilizer plant and Chongqing, Shanghai with small sample: invention product solvability at normal temperatures is good, dissolution time short (5-10 minute); Solubleness in methyl alcohol 〉=5 restrain/100 milliliters; Formaldehyde solution about 37% (pure content≤5%) adds 10,20,30,40 respectively, 50PPM, and under-32 ℃ of temperature, outdoor storage is after 20 days, and is still limpid transparent, finds to generate any throw out.
Embodiment 1:
In 500 liters of enamel stills of band condenser, once drop into 87.5 kilograms of VAC and 262.5 kilograms of methyl alcohol.Material is heated to 55 ℃, once add the methanol solution that contains 0.0875 kilogram of initiator, backflow polymerization 14 hours is warming up to 70 ℃, feed pressurized air in still in the material with recovery part methanol solvate and unreacted VAC (being directly used in next polymerization after the recovery) with pressure 〉=0.2MPa.Get material analyzing in the still, the content of PVAC is 43.88%, starts stirrer, adds 90% acetaldehyde of metering and 9.6 kilograms sulfuric acid simultaneously, after stirring, is warming up to 65 ℃; Under this temperature, reacted 40 minutes, after being chilled to room temperature again, pour the reaction solution of acetal into first header tank, reaction solution enters the liquor kalii acetici that contains excessive KOH through porous second header tank from first header tank with steady flow again, under the shear action of homogenizer, product is separated out with the fine particulate resin; Be total to washing by soaking 24 hours with cold water, changed once washing water in per 6 hours, dry under drying room 50-60 ℃ again through centrifuge dripping, promptly get the finished product--formol polymerization retarder.
Embodiment 2:
Methanol concentration is 75%, initiator A IBN consumption is 0.125%, and the consumption of the catalyzer vitriol oil is 9.0%, 55 ℃ of temperature of reaction.Other condition is with embodiment 1.
Embodiment 3:
Methanol concentration is 80%, and initiator A IBN consumption is 0.15%, and the consumption of the catalyzer vitriol oil is 9.0%, 60 ℃ of temperature of reaction.Other condition is with embodiment 1.
Claims (3)
1, a kind of preparation method of high performance formol polymerization retarder, comprise the polymerization of vinyl acetate between to for plastic, solvent recuperation, acetalation, in and moulding, washing, drying and finished product packing, it is characterized in that in the polymerization technique of vinyl acetate between to for plastic, the consumption of initiator Diisopropyl azodicarboxylate is 0.1～0.15% (wt) of vinyl acetate between to for plastic consumption, the concentration of employed methanol solvate is 75-80% (Wt), the temperature of polyreaction is 55-60 ℃, the consumption of the catalyzer vitriol oil that uses in acetalation is the 8.5-9.5% (Wt) of Vinyl Acetate Copolymer, adopt pressurized air to reclaim solvent methanol, in and be provided with two header tanks in the moulding process.
2, method according to claim 1, the consumption that it is characterized in that the initiator Diisopropyl azodicarboxylate are 0.125～0.15% (Wt) of vinyl acetate between to for plastic consumption.
3, method according to claim 1 is characterized in that the 9.0-9.5% (Wt) of the consumption of the catalyzer vitriol oil that uses as Vinyl Acetate Copolymer in acetalation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94109260A CN1042542C (en) | 1994-08-16 | 1994-08-16 | High performance formol polymerization retarder and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94109260A CN1042542C (en) | 1994-08-16 | 1994-08-16 | High performance formol polymerization retarder and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1124742A CN1124742A (en) | 1996-06-19 |
| CN1042542C true CN1042542C (en) | 1999-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94109260A Expired - Fee Related CN1042542C (en) | 1994-08-16 | 1994-08-16 | High performance formol polymerization retarder and preparing process thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295719A (en) * | 2011-05-06 | 2011-12-28 | 宋道淮 | Novel process for synthesizing formaldehyde stabilizer |
| CN102746126B (en) * | 2012-07-23 | 2015-04-08 | 国药集团化学试剂有限公司 | 2,5-dihydroxybenzoylchloride-SBA-15 polymerization inhibitor, preparation method and application thereof |
| CN108503808A (en) * | 2018-04-18 | 2018-09-07 | 西陇科学股份有限公司 | A kind of water solubility formol polymerization retarder and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085099A (en) * | 1973-04-13 | 1978-04-18 | Produits Chimiques Ugine Kuhlmann | Water-insoluble nitrophenylazophenyl compounds containing a terminal --N--(C2)n --O--CO-- or --CO--O--CH2 --CH2 --C3 F5 group |
| US4085079A (en) * | 1977-02-02 | 1978-04-18 | Monsanto Company | Formaldehyde solutions stabilized with interpolymers of vinyl acetate, vinyl acetal and vinyl alcohol |
| JPS6136303A (en) * | 1984-07-27 | 1986-02-21 | Nippon Kasei Kk | Preparation of agent for stabilizing aqueous solution of formaldehyde |
| CN1053615A (en) * | 1990-06-05 | 1991-08-07 | 湖南省维尼纶厂 | Commercial process of formaldehyde anti-polymerization agent |
-
1994
- 1994-08-16 CN CN94109260A patent/CN1042542C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085099A (en) * | 1973-04-13 | 1978-04-18 | Produits Chimiques Ugine Kuhlmann | Water-insoluble nitrophenylazophenyl compounds containing a terminal --N--(C2)n --O--CO-- or --CO--O--CH2 --CH2 --C3 F5 group |
| US4085079A (en) * | 1977-02-02 | 1978-04-18 | Monsanto Company | Formaldehyde solutions stabilized with interpolymers of vinyl acetate, vinyl acetal and vinyl alcohol |
| JPS6136303A (en) * | 1984-07-27 | 1986-02-21 | Nippon Kasei Kk | Preparation of agent for stabilizing aqueous solution of formaldehyde |
| CN1053615A (en) * | 1990-06-05 | 1991-08-07 | 湖南省维尼纶厂 | Commercial process of formaldehyde anti-polymerization agent |
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| Publication number | Publication date |
|---|---|
| CN1124742A (en) | 1996-06-19 |
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Granted publication date: 19990317 Termination date: 20130816 |