CN1019583B - Technology for producing polyvinyl formal glue from waste vinylon - Google Patents
Technology for producing polyvinyl formal glue from waste vinylonInfo
- Publication number
- CN1019583B CN1019583B CN90105618A CN90105618A CN1019583B CN 1019583 B CN1019583 B CN 1019583B CN 90105618 A CN90105618 A CN 90105618A CN 90105618 A CN90105618 A CN 90105618A CN 1019583 B CN1019583 B CN 1019583B
- Authority
- CN
- China
- Prior art keywords
- vinylon
- adhesive
- formaldehyde
- polyvinyl acetal
- waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a technological process for preparing polyvinyl formal adhesive by waste vinylon, which is characterized in that waste vinylon whose mole hydroformylation degree is from 21 to 50% is hydrolyzed, which enables the mole hydroformylation degree to be reduced below 21% so as to generate the polyvinyl formal adhesive. In the previous reaction, a small amount of hydrochloric acid and a small amount of polyvinyl alcohol are needed, and moreover, when temperature is higher than or equal to 115DEGC, the process of hydrolysis can be promoted. When the pH value of the adhesive is equal to 7, the solid content of the adhesive is 9.23%, and at the temperature of 23.5 DEG C, the viscosity of the adhesive is 1825 centipoises. At the temperature higher than 0DEGC, the adhesive can not be coagulated, and thus, the adhesive can be used as construction adhesive.
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, 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 binder.
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 general, 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 〉=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, the many Ilyushin works of M, P., Jin Jichun etc. translate.Chemical Industry Press (1985), P266～267.
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.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 ℃ (minute-pressure) promotes said hydrolyzed down in temperature 〉=115.Principal reaction is as follows:
(1) the vinylon partial hydrolysis generates formaldehyde polyvinyl acetal
(vinylon)
(formaldehyde polyvinyl acetal)
(2) simultaneously, the formaldehyde reaction of a spot of polyvinyl alcohol and said hydrolyzed generation also generates 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 production.
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 is purging valve, and 2 is Watch glass, and 3 is beaker, and 4 is reactant, and 5 is water, and 6 is tensimeter, and 7 is safety valve, and 8 is portable sterilizer, and 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, with 0.8 * 10
5The steam-heated cal(l)andria of handkerchief (Pa) through 1.5～2 hours, is reduced to normal pressure, takes out beaker 3, adds an amount of water and glue and stirs evenly, and is neutralized to PH=7 with an amount of ammoniacal liquor again, continues to stir evenly, and promptly gets 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, solution is heated to boiling by the time, add 40 kilograms on the short yarn of the useless vinylon of cleaning, build feeding cover, start anchor stirrer 3, with 〉=0.8 * 10
5The steam of the vapor pressure of handkerchief (Pa) feeds steam-gas inlet 1 and 8(comprises interior 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 (1)
1, the useless vinylon of a kind of usefulness is made the processing method of formaldehyde polyvinyl acetal, it is characterized in that useless vinylon is placed the dilute hydrochloric acid solution that is dissolved with a small amount of polyvinyl alcohol, 〉=115 ℃, 〉=0.8 * 10
5Under handkerchief (Pa) heating condition, promote the said hydrolyzed reaction, through 1.5～4 hours, 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.
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 CN1054093A (en) | 1991-08-28 |
| CN1019583B true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928532B (en) * | 2010-05-28 | 2011-12-28 | 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 |
| 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 |
| 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 |
-
1990
- 1990-02-13 CN CN90105618A patent/CN1019583B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1054093A (en) | 1991-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1037850C (en) | Biodegradable resins and a process for the preparation thereof | |
| CN1019583B (en) | Technology for producing polyvinyl formal glue from waste vinylon | |
| CN106750179A (en) | A kind of preparation method of enzymolysis xylogen base epoxy | |
| CN111205372B (en) | The preparation method of cellulose acetate propionate | |
| CN117736488A (en) | cellulose-SiO 2 Preparation method of composite aerogel | |
| CN113603968A (en) | Toughening modified PP plastic particle | |
| CN111484608B (en) | A kind of preparation method of long-term stable production of PBT resin | |
| CN118480273A (en) | A degradable composite material and preparation method thereof | |
| CN101367940A (en) | Preparation method for small-numerator hydroxyl silicone oil | |
| US1960812A (en) | Manufacture of furfur | |
| CN113754536B (en) | Preparation method of triethylene glycol di-n-caprylate | |
| CN114853590A (en) | Novel polyformaldehyde depolymerization method | |
| CN116162263A (en) | Aldehyde lignin and preparation method and application thereof | |
| CN1031090A (en) | Reduce the method for free formaldehyde content in the water-soluble poval methylal resin | |
| CN116332951A (en) | A kind of preparation method and application of isosorbide base diacid | |
| CN105295061A (en) | Thermosensitive polymer containing heavy metal chelating group and its preparation method and application | |
| KR101782967B1 (en) | Preparation method for volatile organic composite containing bio alchol using water soluble polymer cellulose or alginate, or polysaccharide and volatile organic composite processing apparatus using the same | |
| CN1216090C (en) | Chemical Synthesis of Completely Degradable Plastic Poly-β-Hydroxybutyrate | |
| CN115901541A (en) | Method for measuring cellulose content in production wastewater of methylcellulose and derivatives thereof | |
| Watanabe et al. | A Study of Unnatural Amino Acids and Their Peptides. I. The Synthesis of DL-β-(2-Furyl)-α-alanine | |
| KR970059192A (en) | Method for producing polyvinyl alcohol | |
| CN116554520B (en) | Polyethylene composite plastic film containing europium light conversion agent and preparation process thereof | |
| CN1067695C (en) | Process for preparing ethylene-vinylacetate-vinyl alcohol ternary atactic copolymer | |
| CN1128229C (en) | Process for preparing chrome tanning agent from organic waste containing cellulose | |
| CN86106758A (en) | A kind of synthetic method of resol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |