CN1054093A - Use technology for producing polyvinyl formal glue from waste vinylon - Google Patents
Use technology for producing polyvinyl formal glue from waste vinylon Download PDFInfo
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- CN1054093A CN1054093A CN90105618A CN90105618A CN1054093A CN 1054093 A CN1054093 A CN 1054093A CN 90105618 A CN90105618 A CN 90105618A CN 90105618 A CN90105618 A CN 90105618A CN 1054093 A CN1054093 A CN 1054093A
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- vinylon
- polyvinyl acetal
- formaldehyde
- useless
- polyvinyl alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention is the processing method of the useless vinylon system formaldehyde polyvinyl acetal of a kind of usefulness, and mole hydroformylation degree is hydrolyzed at 21～50% useless vinylon, its mole hydroformylation degree is reduced to below 21%, the generation formaldehyde polyvinyl acetal.In this reaction, need with small amount of hydrochloric acid and a small amount of polyvinyl alcohol, and, temperature greater than, equal 115 ℃ and promote hydrolysis down.This glue pH value equals at 7 o'clock, and its solids content is 9.23%, and under 23.5 ℃, viscosity is 1825 centipoises, can not condense more than 0 ℃, can do gluewater in use for construction.
Description
The present invention is the processing method that the useless vinylon of a kind of usefulness is made formaldehyde polyvinyl acetal, the vinylon that it is characterized in that giving up places the dilute hydrochloric acid solution that is dissolved with a small amount of polyvinyl alcohol, greater than, equal under 115 ℃ of (minute-pressure) conditions, make and the molten mixed formaldehyde polyvinyl acetal of water.
Goods formaldehyde polyvinyl acetal of the present invention is a kind of organic polymer polycondensation tackiness agent.
Making formaldehyde polyvinyl acetal in the past is to add water with polyvinyl alcohol, be heated to closely and boil, make the aqueous solution earlier, then add small amount of hydrochloric acid, add formaldehyde, according to general report, the formaldehyde consumption is 40% of a polyvinyl alcohol dry weight, under the condition of normal pressure and 90 ℃, make formaldehyde polyvinyl acetal through more than half a hour.
Vinylon also is to generate polyvinyl formal by polyvinyl alcohol and formaldehyde reaction, and it is insoluble to cold water and boiling water.
The present invention has studied vinylon and formaldehyde polyvinyl acetal, and they both mainly are hydroformylation degree difference on chemical ingredients, and the hydroformylation degree of formaldehyde polyvinyl acetal is generally in the 21%(molecular fraction) below, and vinylon hydroformylation degree is 21～50%.
The present invention with make in the past that formaldehyde polyvinyl acetal is different following 4 points:
1, the present invention has replaced the very expensive polyvinyl alcohol of price of usefulness in the past with cheap useless vinylon.
2, the present invention does not use formaldehyde, like this, has both saved starting material, has reduced environmental pollution again.
3, the present invention has used a spot of hydrochloric acid except the same with the past in process of production, also will add a small amount of polyvinyl alcohol, to promote generation and the molten mixed formaldehyde polyvinyl acetal of water.
4, the present invention reacts under greater than 115 ℃ of (minute-pressure) conditions, and the past is to be to react under the condition of normal pressure and 90 ℃ with polyvinyl alcohol and formaldehyde reaction system formaldehyde polyvinyl acetal.
Two pieces of pertinent literatures that are in the search report that was provided on November 24th, 1 according to examination department of Patent Office of the People's Republic of China retrieval service analyze as follows:
First piece " organic chemistry ", volume two, D, C.Neck, M, P.Many Ilyushin works, Jin Jichun etc. translate.Chemical Industry Press (1985), P.266～267.
Mention acetal in the book and do in acid under the condition of catalyzer, can hydrolysis generate alcohols and aldehydes, this is the general principles of chemistry, and book passes the imperial examinations at the provincial level is the example of low molecule acetal hydrolysis.Be not the example of polymer acetal hydrolysis, in fact, to come hydrolysis be very difficult to high molecular polyvinyl formal really with very rare acid under normal pressure, and vinylon is what can not generate with the molten mixed glue of water under the condition of general acid hydrolysis.Above-mentioned " organic chemistry " both do not spoken of with vinylon and made polyvinyl alcohol glue, more do not have a concrete processing method of in industrial production, making.Because there is not concrete technical scheme, therefore, production can't be carried out, and the present invention is with useless vinylon system formaldehyde polyvinyl acetal, and concrete producing and manufacturing technique is arranged, and under certain conditions, can generate and the molten mixed glue of water, and can carry out mass production.
Second piece of Japan's special permission communique, clear 48-18579 " with the method for the broken silk making of vinylon polyvinyl acetal resin product ".
The method of above-mentioned patent is that vinylon is continued hydroformylation, improves the hydroformylation degree, generates mole hydroformylation degree at (even generating mole hydroformylation degree 87～88%) water-fast solid resin more than 55%.And the present invention is opposite with aforesaid method, is not to continue hydroformylation, but makes acetal do partial hydrolysis, reduces its hydroformylation degree, generation can with the molten mixed formaldehyde polyvinyl acetal of water.
Second point, above-mentioned method will be with a lot of acid, and only sulfuric acid will be used 80% of vinylon weight, also have acetic acid will use 4.5 times of vinylon weight.The present invention is different with above-mentioned method, as long as use a spot of hydrochloric acid, it is below 12.5% of vinylon weight with the acid amount, and aforesaid method has just become acid with so much acid, result, rather than becomes glue.The present invention, promptly becomes and the molten mixed formaldehyde polyvinyl acetal of water as long as neutralize with a spot of ammoniacal liquor because use the acid amount very few, last, and, gelling can not take place.
To the comparative analysis of above-mentioned two pieces of pertinent literatures, can illustrate that the present invention not only has novelty, and also creative.
The objective of the invention is useless vinylon is made useful formaldehyde polyvinyl acetal, turn waste into wealth.
The producer of a lot of production vinylon is arranged in the whole nation, many waste cottons are all arranged, the vinylon process unit many has many refuse yarns again, and in addition, fishing net factory also has many useless vinylon sometimes, and in a word, the total quantity of useless vinylon is appreciable.
Ultimate principle of the present invention is that mole hydroformylation degree is hydrolyzed at 21～50% useless vinylon, the mole hydroformylation degree of useless vinylon is reduced to below 21%, the generation formaldehyde polyvinyl acetal.In this reaction, need with a spot of hydrochloric acid and a spot of polyvinyl alcohol, and, promote said hydrolyzed in temperature down more than or equal to 115 ℃ (minute-pressures).Principal reaction is as follows:
(1) the vinylon partial hydrolysis generates formaldehyde polyvinyl acetal ...-CH
2-
(vinylon)
(formaldehyde polyvinyl acetal)
(2) simultaneously, the formaldehyde reaction of a spot of polyvinyl alcohol and said hydrolyzed generation also generates formaldehyde polyvinyl acetal.
(polyvinyl alcohol)
(formaldehyde polyvinyl acetal)
But also there is a spot of formaldehyde to emit.
The present invention has following advantage and positively effect with the processing method of the formaldehyde polyvinyl acetal that useless vinylon makes:
1, at technical elements, with the prepared glue of this method, when its pH value equaled 7, solids content was 9.23%, and under 23.5 ℃, the viscosity that records with rotational viscosimeter is 1825 centipoises.This glue can not condense into jelly more than 0 ℃.
This formaldehyde polyvinyl acetal can be done building glue.Can make inner, external wall coating and floor coating with it.
2, at economic aspect, replaced the very expensive polyvinyl alcohol of price with cheap useless vinylon, and saved formaldehyde, by present market value, polyvinyl alcohol is per ton to be more than 9000 yuan, and per ton of useless vinylon at 1,000 yuan to thousands of units.One ton of useless vinylon can replace one ton of polyvinyl alcohol.
3, aspect social, make that producing vinylon all obtains the purposes of doing formaldehyde polyvinyl acetal the same with polyvinyl alcohol with waste material with vinylon processing generation.
Now accompanying drawing of the present invention is explained as follows:
The setting drawing of accompanying drawing 1, making in laboratory formaldehyde polyvinyl acetal.
Among Fig. 1,1 be purging valve, 2 is Watch glass, 3 is beaker, 4 is reactant, 5 is water, 6 is tensimeter, 7 is safety valve, 8 is portable sterilizer, 9 is coal stove.
Accompanying drawing 2, the industrial setting drawing of making formaldehyde polyvinyl acetal of the enamel reactor.
Among Fig. 2: 1,8 is the water vapour import, and 2 is charging opening, and 3 is anchor stirrer, and 4 is reactant, and 5 is speed reduction unit, and 6 is pressure gauge, and 7,10 is purging valve, and 9 is baiting valve, and 11 is the enamel reactor.
Embodiments of the invention are as follows:
Embodiment 1: laboratory preparation
As shown in Figure 1, in 500 milliliters beaker, add 100 milliliters of the hydrochloric acid solns of 0.25N, add 5 gram polyvinyl alcohol, add a cover Watch glass 2 on the beaker 3, with its be heated in the water-bath complete molten till.Continue to add the hydrochloric acid soln to 150 milliliter of 0.25N, be heated to and boil, add the useless vinylon of 30 grams again, useless vinylon is all soaked in beaker 3 with glass stick, cover Watch glass 2 after, put into portable sterilizer 8.Make portable sterilizer 8 on coal stove 9, use 0.8 kilograms per centimeter
2Steam-heated cal(l)andria, through 1.5～2 hours, reduce to normal pressure, take out beaker 3, add an amount of water and glue and stir evenly, be neutralized to PH=7 with an amount of ammoniacal liquor again, continue to stir evenly, promptly get the glue of required viscosity.
Embodiment 2: industrial technology
As shown in Figure 2, in the enamel reactor 11 of 500 liters, put into and be dissolved with 〉=200 kilograms of the aqueous solution of 5 kilograms of polyvinyl alcohol, add 5 kilograms of concentrated hydrochloric acids again, stir evenly, logical steam-heated cal(l)andria in interlayer, by the time solution is heated to boiling, and adds 40 kilograms on the short yarn of the useless vinylon of cleaning, and builds feeding cover, start anchor stirrer 3, with 〉=0.8 kilograms per centimeter
2The steam of vapor pressure feed steam-gas inlet 1 and 8(comprise in pot and interlayer).Through 3.5～4 hours, can see that from the photoscope of enamel reactor 11 glue makes, slowly step-down is when normal pressure, open feeding cover, add an amount of water, and stirred, add proper ammonia and be neutralized to PH=7, continue to stir evenly, can make the glue of required viscosity.
Required steam can with 0.2 ton/time vapor volume one in E level boiler provide.Have anchor stirrer in the enamel reactor of 500 liters.
Claims (2)
1, the useless vinylon of a kind of usefulness is made the processing method of formaldehyde polyvinyl acetal, the vinylon that it is characterized in that giving up places the dilute hydrochloric acid solution that is dissolved with a small amount of polyvinyl alcohol, greater than, equal under 115 ℃ of (minute-pressure) heating conditions, promote the said hydrolyzed reaction, through appropriate time, promptly can be made into and the molten mixed formaldehyde polyvinyl acetal of water, be chilled to normal pressure, after adding an amount of water and stirring evenly, add proper ammonia again and be neutralized to PH=7, continue to stir evenly, can make the formaldehyde polyvinyl acetal of required viscosity.
2, according to claim 1, above-mentioned useless vinylon in the dilute hydrochloric acid solution of a small amount of polyvinyl alcohol Heating Characteristics for adopt greater than, equal 0.8 kilograms per centimeter
2Vapor pressure heating 1.5～4 hours, to promote that hydrolysis reaction carries out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105618A CN1019583B (en) | 1990-02-13 | 1990-02-13 | Technology for producing polyvinyl formal glue from waste vinylon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105618A CN1019583B (en) | 1990-02-13 | 1990-02-13 | Technology for producing polyvinyl formal glue from waste vinylon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054093A true CN1054093A (en) | 1991-08-28 |
| CN1019583B CN1019583B (en) | 1992-12-23 |
Family
ID=4879428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90105618A Expired CN1019583B (en) | 1990-02-13 | 1990-02-13 | Technology for producing polyvinyl formal glue from waste vinylon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019583B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928532A (en) * | 2010-05-28 | 2010-12-29 | 国电英力特能源化工集团股份有限公司 | Method for producing high-viscosity adhesive from polyvinyl alcohol high-strength high-modulus waste fiber |
| CN102173493A (en) * | 2011-03-08 | 2011-09-07 | 北京市环境保护科学研究院 | Process for removing polyvinyl alcohol in waste water |
| CN103555227A (en) * | 2013-11-07 | 2014-02-05 | 湖南神力铃胶粘剂制造有限公司 | Adhesive made of waste silks of vinylon and preparation method thereof |
| CN115246954A (en) * | 2022-01-24 | 2022-10-28 | 浙江理工大学 | Method for efficiently recovering polyvinyl alcohol in waste polyvinyl formal products |
-
1990
- 1990-02-13 CN CN90105618A patent/CN1019583B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928532A (en) * | 2010-05-28 | 2010-12-29 | 国电英力特能源化工集团股份有限公司 | Method for producing high-viscosity adhesive from polyvinyl alcohol high-strength high-modulus waste fiber |
| CN102173493A (en) * | 2011-03-08 | 2011-09-07 | 北京市环境保护科学研究院 | Process for removing polyvinyl alcohol in waste water |
| CN103555227A (en) * | 2013-11-07 | 2014-02-05 | 湖南神力铃胶粘剂制造有限公司 | Adhesive made of waste silks of vinylon and preparation method thereof |
| CN103555227B (en) * | 2013-11-07 | 2015-08-12 | 湖南神力铃胶粘剂制造有限公司 | A kind of tackiness agent utilizing vinylon waste silk to prepare and preparation method thereof |
| CN115246954A (en) * | 2022-01-24 | 2022-10-28 | 浙江理工大学 | Method for efficiently recovering polyvinyl alcohol in waste polyvinyl formal products |
| CN115246954B (en) * | 2022-01-24 | 2023-11-24 | 浙江理工大学 | High-efficiency recovery method of polyvinyl alcohol in waste polyvinyl formal product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1019583B (en) | 1992-12-23 |
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