CN1053615A - Commercial process of formaldehyde anti-polymerization agent - Google Patents
Commercial process of formaldehyde anti-polymerization agent Download PDFInfo
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- CN1053615A CN1053615A CN 90105480 CN90105480A CN1053615A CN 1053615 A CN1053615 A CN 1053615A CN 90105480 CN90105480 CN 90105480 CN 90105480 A CN90105480 A CN 90105480A CN 1053615 A CN1053615 A CN 1053615A
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Abstract
A kind of synthetic method of novel methylene stopper is: with VAC, MeOH is raw material, and AIBN is an initiator, and in the enamel reaction still of 5001 band condensers, polymerization makes the PVAC resin liquid that viscosity-average molecular weight is 17000-45000.Behind N expeling partial solvent, the acetal reaction and then is hydrolyzed.Reaction product is separated out particulate resins through the moulding of high-speed stirring dispersion machine, through washing, drying, promptly makes acetyl-containing 10～15% (wt), the stopper of acetal base 50～70% (wt) again.
Description
The present invention relates to the synthetic method of novel methylene stopper-polyvinylacetal.Industrial formol can become muddy gradually under low temperature or longer storage, and generates the white precipitate of polyoxymethylene.The processing that has a strong impact on product is used and is carried.For preparation with stable formalin is provided, once studied both at home and abroad and used multiple stopper, as alcohol compounds such as methyl alcohol, propyl alcohol.Urea and trimeric cyanamide compounds; Hydrazine hydrate, the Soxylat A 25-7 compounds of water soluble cellulose and high fatty alcohol etc.Recent patent DT3411,416, reports such as JP6136303, US4085.079, for raw material comes the synthesizing formaldehyde stopper, but do not see commodity selling as yet with VAC, PVA, formaldehyde or acetaldehyde etc. by above-mentioned patented technology production.One of target of the present invention is with reference to the VS4085079 technology, in conjunction with our factory's actual augmentation and improve synthetic technology, sets up industrial production device, realizes the suitability for industrialized production of stopper.Another target of the present invention is that the stopper of producing is mainly used in domestic 37% left and right sides industrial formol aqueous solution, to replace consumption very big formol polymerization retarder and quality product restive, solubility property is poor, the VAC-tetracol phenixin telomer stopper that color and luster is very dark, and prevent that effectively formaldehyde is in the winter time under the low tempertaure storage, do not generate polymkeric substance, in order to the conveying and the use of formaldehyde.
One of characteristics of the present invention are to utilize the 500l of a band condenser or the enamel reaction still of 200l, prepare satisfactory PVAC resin liquid earlier, under 50 ℃, use N
2Blow catch up with partial solvent and unreacted VAC after, the acetalation that and then is hydrolyzed makes and closes the acetalation product that symbol requires.Blow out recovered solvent without any refining, can be used further to polymerization.
Two of characteristics of the present invention are that resin molding method is very simple and effective.The product of own acetalation need only be flow into from the header tank of perforated plate in the acetum of KOH, start the high-speed stirring dispersion machine simultaneously, under its high speed centrifugation shear action, product is very fast separates out with the fine-grannular resin.
Three of characteristics of the present invention are to use our factory high density by-product acetaldehyde to do the acetalation agent, and its purity is greater than 98%.
Four of characteristics of the present invention can be dry in less than 50 ℃ fluidized-bed through the wet resin of centrifuge dripping.
Five of characteristics of the present invention, acetalation are to carry out in normal-pressure reaction kettle.
Its constitutional features of the stopper of system of the present invention is as follows:
Wherein, in the macromole, vinyl acetal base is 50～70%(wt)
In the macromole, the vinyl ethanoyl is 10～15%(wt)
Other is the ethene alcohol radical.
Principle process of the present invention such as accompanying drawing, its master operation comprises:
(1) polymerization-material is heated to 60～65 ℃ divides secondary to add initiator methanol solution, backflow polymerization 10hr.
(2) drive solvent-drive partial solvent and unreacted VAC, reclaim and be used for next polymerization.
(3) the PVAC methanol solution of hydrolysis of acetalsization-will concentrate is cooled to 10～15 ℃, adds 98% the acetaldehyde and the H of metering
2SO
4, after stirring, be warming up to 60 ℃ of reactions 35 minutes, be cooled to the room temperature discharging.
(4) elutriation-refrigerative acetal resin material is poured in the header tank with holes allows it flow in the HAC aqueous solution of KOH of PH:12, starts the high-speed stirring dispersion machine simultaneously, and product splits out rapidly with white fine particulate resin.
(5) 6 washing resins of washing-usefulness cold water.
(6) centrifuge dripping.
(7) dry-in fluidized-bed, dry below 50 ℃.
Its application characteristic of the stopper that the present invention makes is as follows:
Under the normal temperature, stir a little, promptly may be dissolved in the methyl alcohol, the solubleness in methyl alcohol is not less than 10g/100ml, the solution water white transparency, in about 37% formalin, (wherein contain methyl alcohol below 2%), add this stopper of 10PPM, under-13～-18 ℃, store after 37 days, stored at normal temperatures 15 months, solution still transparent clear sediment-free generates again.
Below with example explanation the present invention:
In the 500l enamel still in the band condenser, once drop into 105kgVAC and 245kgMeOH, material is heated to 60～65 ℃, the initiator methanol solution that adds 1/2 total amount behind the backflow polymerization 4hr, adds residual A IBN initiator again, backflow polymerization 6hr is cooled to below 50 ℃, logical N
2In the material, to drive partial solvent and unreacted VAC, recovered solvent is used for next polymerization in still.Get material analyzing in the still, PVAC is 59.74%, and molecular-weight average is 39560, is cooled to 10～15 ℃, the acetaldehyde 26.2kg of adding 98% and the H of metering
2SO
4, after stirring, be warming up to 60 ℃, reacted 35 minutes, be cooled to the room temperature discharging.The good material of the own acetal of refrigerative is poured in the header tank of perforated plate, allow it flow among the KOH and the HAC aqueous solution of PH:12, start the high-speed stirring dispersion machine simultaneously, under the high speed centrifugation shear action, product is separated out rapidly with white fine particulate resin, behind six washing resins of cold water, through centrifuge dripping, in fluidized-bed, dry below 50 ℃, get product.
Claims (5)
1, a kind of viscosity-average molecular weight 17000～45000 (in VAC); Contain vinyl acetal base 50～70%, vinyl, ethanoyl 10～15%, other is the industrial production process of the novel methylene stopper of ethene alcohol radical, it is characterized in that in the technological process, comprises following processing step:
The solution polymerization of 1-1 vinyl acetate between to for plastic
Concentrating and solvent recuperation of 1-2 polyvinyl acetate resin liquid
The hydrolysis-condensation reaction of 1-3 Vinyl Acetate Copolymer
The aftertreatment of 1-4 acetal resin liquid
2, according to claim 1 described method, it is characterized in that: vinyl acetate between to for plastic is that initiator carries out polymerization with AIBN in methyl alcohol, 60～65 ℃ of polymerization temperatures, polymerization time is 6～12hr, VAC:MeOH=30: 40: 60～70, the VAC transformation efficiency is greater than 70%, and the PVAC viscosity-average molecular weight is 17000～45000.
3, according to claim 1 described method, it is characterized in that: polyvinyl acetate resin liquid is concentrated into 50～65% by 20～30%, temperature＜50 ℃ when concentrating, and remaining VAC is lower than 0.005%, and recovered solvent need not be made with extra care, and is used for the polymerization of 1-1.
4, according to claim 1 described method, it is characterized in that: with dense H
2SO
4Being catalyzer, is the acetalation agent with 98% dense acetaldehyde, under (acetaldehyde is this plant by-products, and purity is greater than 98%) normal pressure, and reaction 0.5～1h, 10～60 ℃ of temperature of reaction, the acetal base is 50～70% in the control macromole, ethanoyl 10～15%(is by weight).
5, according to claim 1 described method, it is characterized in that: aftertreatment comprises resin forming washing, drying.During moulding, resin liquid from the header tank with porous web plate, in the acetum of inflow KOH (PH=11～12), under the centrifugal shear knife effect of high-speed stirring dispersion machine, is separated out the tiny particulate resins of white rapidly.The resin of separating out is removed remaining H with six washings of cold water
2SO
4And acetaldehyde, behind the centrifuge dripping, put in the fluidized drying device again, dry below 50 ℃, get product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105480 CN1024280C (en) | 1990-06-05 | 1990-06-05 | Industrial preparation method of formaldehyde polymerization inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105480 CN1024280C (en) | 1990-06-05 | 1990-06-05 | Industrial preparation method of formaldehyde polymerization inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1053615A true CN1053615A (en) | 1991-08-07 |
| CN1024280C CN1024280C (en) | 1994-04-20 |
Family
ID=4879294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90105480 Expired - Fee Related CN1024280C (en) | 1990-06-05 | 1990-06-05 | Industrial preparation method of formaldehyde polymerization inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024280C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042542C (en) * | 1994-08-16 | 1999-03-17 | 李瑞林 | High performance formol polymerization retarder and preparing process thereof |
| CN102746126A (en) * | 2012-07-23 | 2012-10-24 | 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 |
-
1990
- 1990-06-05 CN CN 90105480 patent/CN1024280C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042542C (en) * | 1994-08-16 | 1999-03-17 | 李瑞林 | High performance formol polymerization retarder and preparing process thereof |
| CN102746126A (en) * | 2012-07-23 | 2012-10-24 | 国药集团化学试剂有限公司 | 2,5-dihydroxybenzoylchloride-SBA-15 polymerization inhibitor, preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024280C (en) | 1994-04-20 |
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