CN101875834A - Method for synthesizing aqueous adhesive for processing wood by using polyester reclaiming material - Google Patents
Method for synthesizing aqueous adhesive for processing wood by using polyester reclaiming material Download PDFInfo
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- CN101875834A CN101875834A CN2009100501112A CN200910050111A CN101875834A CN 101875834 A CN101875834 A CN 101875834A CN 2009100501112 A CN2009100501112 A CN 2009100501112A CN 200910050111 A CN200910050111 A CN 200910050111A CN 101875834 A CN101875834 A CN 101875834A
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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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Abstract
The invention relates to a preparation method for synthesizing aqueous adhesive for processing wood by using a polyester reclaiming material. The adhesive is prepared from aqueous solution or aqueous dispersion of aqueous polyester polyol or polyester polyacid synthesized by alcoholysis of the polyester reclaiming material, and the adhesive can be separately used as aqueous adhesive or reacted with a special structural cross linker to form aqueous adhesive with better mechanical property and water resistance. The aqueous adhesive has the characteristics of environmental protection and economy, and has excellent adhesive strength and heat resistance in the fields of processing the wood into shaving boards, directional shaving boards, medium-density fiber boards, laminated wood, various composite boards, surface decorating boards and the like.
Description
Technical field:
The present invention relates to a kind of preparation method who utilizes the polyester reclaiming material synthesizing aqueous adhesive for processing wood
Background technology:
The a large amount of polyester reclaiming material that produces in daily life and the production not only causes environmental pollution, and has caused great waste of material.Therefore, reclaim polyester waste material energetically and fully utilize, have very big value on considering with environmental protection economically.
A large amount of polyvalent alcohols that made by terylene waste material have appearred on the urethane market along with American-European countries, polyester waste material alcoholysis synthesizing polyester polyvalent alcohol technology with low cost has obtained development rapidly, but utilize the tackiness agent of polyester reclaiming material synthetic polyester polyol preparation that report is also arranged, example is at US 7,157, designed two-step reaction in 139: the first step is with reclaiming the modification polymer of PET material with synthetic terminal hydroxy group of all monomers in addition or end carboxyl, second step and PET or other polycondensate carry out transesterification reaction, obtain polyester adhesive.
At present, though it is a lot of to can be used for the tackiness agent kind of timber industry, mainly be that " three-aldehyde glue " occupies an leading position at present, account for about 90% of whole timber industry tackiness agent consumption." yet three-aldehyde glue " be release formaldehyde in use, serious harm healthy to people, and research and development are efficient, the development trend that becomes the timber industry field of environmental friendliness and cheap tackiness agent.The present invention mainly is the aqueous adhesive of being used by polyester reclaiming material synthetic polyester type wood working, environmental protection and economy not only, and have good anti-hydrolytic performance, bonding strength and thermotolerance.
Summary of the invention:
The invention provides a kind of preparation method who reclaims the synthetic aqueous adhesive of polyester waste material that utilizes, belong to the wood working adhesive area.Its purpose is to utilize the alcoholysis recovery technology of polyester reclaiming material, the synthetic polyester polyol has the segment of terephthalic acid, therefore the waterborne polyester material that is made by the polyester polyol among the present invention has good anti-hydrolytic performance, the advantage that has economic environmental protection simultaneously is applied in the wood working adhesive area and has excellent bonding strength and good heat resistance.
Polyester reclaiming material synthesizing aqueous adhesive for processing wood of the present invention is by polyester reclaiming material alcoholysis synthetic waterborne polyester polyvalent alcohol or polyester polyols aqueous acid or aqueous dispersions, gets with the linking agent of special construction is mutually mixed.
The aqueous solution of polyester reclaiming material alcoholysis synthetic polyester polyol of the present invention or the method for aqueous dispersions are as follows: with polyester waste material; polyvalent alcohol; m-phthalic acid dibasic ester-5-sodium sulfonate; drop in reactor at by weight ratio 1: 1.5-10: 0.1~1; add catalyzer; under nitrogen protection; stir and progressively intensification; between 180-250 ℃, carry out alcoholysis and transesterification reaction; there is the small molecules cut to produce; reaction to do not have that cut produces and system becomes evenly till; be the terminal point of alcoholysis, steam and remove unnecessary polyvalent alcohol, obtain polyester polyol; add quantitative water, the preparation mass concentration is 10~100% the aqueous solution or aqueous dispersions.
The method of polynary aqueous acid of polyester reclaiming material alcoholysis synthesizing polyester of the present invention or aqueous dispersions is as follows: the polyester polyol that aforesaid method is made, measure hydroxyl value, hydroxyl value according to polyester polyol, the mol ratio that adds metering is polyprotonic acid or the multi-anhydride of alcohol/acid=1-10, reacts between 160-230 ℃, has water to distillate, reaction is not till have an overhead product, obtain polyester polyols acid, add quantitative water, the preparation mass concentration is 10~100% the aqueous solution or aqueous dispersions.
As required, can in the aqueous systems of aqueous adhesive of the present invention, add additive and auxiliary agent commonly used.For example: stiffening agent, pigment, dyestuff, antitack agent, dispersion stabilizer, viscosity modifier, levelling agent, anti-gelating agent, photostabilizer, oxidation inhibitor, UV light absorber, inorganic and organic filler, softening agent, lubricant, antistatic agent, toughener, catalyzer etc.
Embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
1) polyester reclaiming material synthesizing polyester polyatomic alcohol water solution: have thermometer at one, agitator, in the four-hole boiling flask of nitrogen ingress pipe and fractionation plant, drop into glycol ether 28g successively, neopentyl glycol 12g, PET polyester bottles fragment 49.9g, dimethyl isophthalate-5-sodium sulfonate 10g, tetrabutyl titanate is as catalyzer 0.1g.Feed under the situation of nitrogen and be warming up to 240 ℃ gradually, the fractionation column temperature is lower than 105 ℃, keeps this temperature all to disappear until the polyester waste material particle, when reacting the transparent terminal point that is alcoholysis till evenly that becomes to system, steams and removes the unnecessary about 2.4g of polyvalent alcohol.Recording hydroxyl value is 118mgKOH/g.Be cooled to room temperature, add the water of 244g, the preparation mass concentration is 40% the aqueous solution.
2) the above-mentioned first component 200g is mixed mutually with 19.6g isophorone diisocyanate linking agent, blending ratio is: the mass ratio of first component and linking agent is, first component: linking agent=100: 9.8, add catalyzer dibutyl tin dilaurate 0.4g and water 30g, to not detecting nco value, promptly obtain the waterborne polyester tackiness agent aqueous dispersions that 40% wood working is used 80 ℃ of abundant reactions for extremely.
Embodiment 2
1) the polyester reclaiming material synthesizing polyester polyprotonic acid aqueous solution: have thermometer at one, agitator, in the four-hole boiling flask of nitrogen ingress pipe and fractionation plant, drop into ethylene glycol 12g successively, glycol ether 40g, dimethyl isophthalate-5-sodium sulfonate 8g, PET polyester bottles fragment 39.9g, tetrabutyl titanate is as catalyzer 0.1g.Feed under the situation of nitrogen and be warming up to 240 ℃ gradually, the fractionation column temperature is lower than 105 ℃, keeps this temperature all to disappear until the polyester waste material particle, when the reaction system all even gradually transparent terminal point that is alcoholysis that becomes.Steam and remove the about 2.7g of unnecessary polyvalent alcohol, recording hydroxyl value is 172mgKOH/g.Be cooled to 180 ℃, add m-phthalic acid 21.0g, being warming up to 220 ℃ reacts to acid number<20mgKOH/g, be cooled to 180 ℃ then, add 8.5g trimellitic acid anhydride reactant 30min, obtain the waterborne polyester polyprotonic acid, acid number is 45.1mgKOH/g, be cooled to room temperature, adding 380.4g water preparation mass concentration is 25% the waterborne polyester polyprotonic acid aqueous solution.
2) the above-mentioned first component 200g is mixed mutually with linking agent N-butyl aziridine 2.3g, dibutyl tin dilaurate 0.2g, water 7.5g, obtain the waterborne polyester tackiness agent that wood working is used, blending ratio is: the mass ratio of first component and linking agent is, first component: linking agent=100: 1.2, fully react till acid number<3mgKOH/g at 80 ℃, promptly obtain the waterborne polyester binder aqueous solution that 25% wood working is used.
Embodiment 3
As the composite floor board adhesive applications, pressing plate: test specimen specification 50 * 50mm, Amount of spread 50-70g/m
2, assembly time 48h, press pressure 10kg/cm
2, clamping time 8~10min, platen temperature normal temperature.
With the composite floor board of above-mentioned preparation, through the pressing plate experiment,, show that bonding effect is good if do not have cracking phenomena behind the assembly time 48h, if there is the part to come unglued or obscission, illustrate that then the bonding effect of this tackiness agent is bad.
Reaching waterborne polyester tackiness agent that test condition uses in the embodiment of the invention 1 and 2 preparation respectively according to the method described above, to carry out composite floor board as tackiness agent bonding, and the result shows that the composite floor board bonding effect of preparation of embodiment 1 and 2 is good, there is no the obscission of coming unglued.
Claims (12)
1. method of utilizing the polyester reclaiming material synthesizing aqueous adhesive for processing wood, this tackiness agent prepares as follows:
1) preparation method of polyester reclaiming material alcoholysis synthetic polyester polyol or polyester polyols aqueous acid or aqueous dispersions:
Polyester reclaiming material alcoholysis synthetic polyester polyols alcohol solution or aqueous dispersions: with polyester waste material; polyvalent alcohol; m-phthalic acid dibasic ester-5-sodium sulfonate; drop in reactor at by weight ratio 1: 1.5-10: 0.1~1; add catalyzer; under nitrogen protection; stir and progressively intensification; between 180-250 ℃, carry out alcoholysis and transesterification reaction; there is the small molecules cut to produce; reaction to do not have that cut produces and system becomes evenly till; be the terminal point of alcoholysis, steam and remove unnecessary polyvalent alcohol, obtain the waterborne polyester polyvalent alcohol; add quantitative water, the preparation mass concentration is 10~100% the aqueous solution or aqueous dispersions.
Or the preparation of polyester reclaiming material alcoholysis synthetic polyester polyols aqueous acid or aqueous dispersions: the polyester polyol that utilizes method for preparing, hydroxyl value according to polyester polyol, the mol ratio that adds metering is polyprotonic acid or the multi-anhydride of alcohol/acid=1-10, between 160-230 ℃, react, have water to distillate, reaction obtains the polyester polyols acid of water-soluble or water dispersible till do not have an overhead product, add quantitative water, the preparation mass concentration is 10~100% the aqueous solution or aqueous dispersions.
2) with the above-mentioned first component polyester polyol or polyester polyols aqueous acid or aqueous dispersions, mix mutually with the linking agent of special construction, obtain the waterborne polyester tackiness agent that wood working is used, blending ratio is: the mass ratio of first component and linking agent is first component: linking agent=100: 1~20.
2. method according to claim 1 is characterized in that polyester polyol or polyester polyols aqueous acid or aqueous dispersions can be: polyester polyols alcohol solution, polyester polyols aqueous acid, polyester polyol aqueous dispersions, polyester polyols sour water dispersion liquid one or more mixture wherein.
3. method according to claim 1 is characterized in that the linking agent of used special construction is: water dispersible polyisocyanates, blocked polyisocyanate, aziridine, carbodiimide, epoxy silane one or more mixtures wherein.
4. by the described method of claim 1, it is characterized in that described polyester reclaiming material is: polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly terephthalic acid ethylene glycol-mutual-phenenyl two acid bromide two alcohol ester's multipolymer, poly terephthalic acid propylene glycol-mutual-phenenyl two acid bromide two alcohol ester's multipolymer, poly terephthalic acid ethylene glycol-propylene glycol ester terephthalate's multipolymer.
5. by the described method of claim 1, it is characterized in that used polyvalent alcohol is a dibasic alcohol: ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, glycol ether, dipropylene glycol, pentanediol, neopentyl glycol, hexylene glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 3,3-glycol (D33 monomer); Or trivalent alcohol and polyvalent alcohol: the mixture of one or more polyvalent alcohols in glycerol, TriMethylolPropane(TMP), trimethylolethane, the tetramethylolmethane.
6. by the described method of claim 1, it is characterized in that used m-phthalic acid dibasic ester-5-sodium sulfonate is that dibasic ester is dimethyl isophthalate-5-sodium sulfonate, dimethyl isophthalate-5-sodium sulfonate, m-phthalic acid dipropyl-5-sodium sulfonate, m-phthalic acid diisopropyl ester-5-sodium sulfonate, m-phthalic acid di-n-butyl-5-sodium sulfonate, m-phthalic acid diisobutyl ester-5-sodium sulfonate, m-phthalic acid two n-pentyl esters-5-sodium sulfonate, m-phthalic acid diisoamyl ester-5-sodium sulfonate, m-phthalic acid two peopentyl esters-5-sodium sulfonate, the just own ester of m-phthalic acid two-5-sodium sulfonate, m-phthalic acid two dissidents ester-5-sodium sulfonate, m-phthalic acid two new own ester-5-sodium sulfonates, m-phthalic acid two cyclohexyls-5-sodium sulfonate.
7. by the described method of claim 1, its feature can be the acetic acid salt at used catalyzer, and titanate ester, organic tin, antimony are any catalyzer in the class, or also can be the composite catalysts of above-mentioned any a few class catalyzer.
8. method as claimed in claim 3, it is characterized in that the water dispersible polyisocyanates is by tolylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 1,12-ten dimethylene diisocyanates, isophorone diisocyanate, ditan 4, the 4-vulcabond, the double-hexyl methane vulcabond, xylylene diisocyanate, naphthalene-1, the 5-vulcabond, Methylcyclohexyl diisocyanate, tetramethylxylylene diisocyanate, and the tripolymer of above-mentioned polyisocyanates and/or biuret, with the substance reaction that helps emulsification or water-dispersion or mix and get.
9. method as claimed in claim 3, it is characterized in that blocked polyisocyanate is by tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-ten dimethylene diisocyanates, isophorone diisocyanate, ditan 4,4-vulcabond, double-hexyl methane vulcabond, xylylene diisocyanate, naphthalene-1,5-vulcabond, Methylcyclohexyl diisocyanate, tetramethylxylylene diisocyanate, and above-mentioned polyisocyanate trimer and/or biuret, get with the encapsulant reaction.
10. method as claimed in claim 3 is characterized in that used carbodiimide is N, N-di-isopropyl carbodiimide, N, N-dicyclohexyl carbodiimide.
11. method as claimed in claim 3 is characterized in that used aziridine is N-methylaziridine, N-butyl aziridine, the 2-methylaziridine.
12. method as claimed in claim 3 is characterized in that used epoxy silane is C
2H
4O (CH
2) nSiX
3(n is an integer, and X is CH
3O, C
2H
5O, CH
3OC
2H
4O).
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101979422A (en) * | 2010-10-15 | 2011-02-23 | 济南大学 | Method for preparing environmentally-friendly macromoleclar polymer and application |
CN102775581A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of novel end isocyanate polyurethane |
CN102775575A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of double-component polyurethane |
CN108818816A (en) * | 2018-04-24 | 2018-11-16 | 广州精点高分子材料制品有限公司 | A kind of ceramics wood and manufacturing method based on closed NCO |
CN109666180A (en) * | 2018-12-21 | 2019-04-23 | 江苏中信世纪新材料有限公司 | A method of using organotin catalysts solution degradation unsaturated polyester material |
WO2019188335A1 (en) * | 2018-03-28 | 2019-10-03 | Dic株式会社 | Reactive adhesive agent, laminate film, and packaging body |
CN113248882A (en) * | 2021-05-25 | 2021-08-13 | 黄山美森新材料科技股份有限公司 | Wear-resistant and impact-resistant plastic-wood material prepared from waste PET (polyethylene terephthalate) bottle and preparation method thereof |
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2009
- 2009-04-28 CN CN2009100501112A patent/CN101875834A/en active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101979422A (en) * | 2010-10-15 | 2011-02-23 | 济南大学 | Method for preparing environmentally-friendly macromoleclar polymer and application |
CN101979422B (en) * | 2010-10-15 | 2012-02-22 | 济南大学 | Method for preparing environmentally-friendly macromoleclar polymer and application |
CN102775581A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of novel end isocyanate polyurethane |
CN102775575A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of double-component polyurethane |
CN102775575B (en) * | 2012-08-17 | 2014-01-15 | 济南大学 | Preparation method and application of double-component polyurethane |
CN102775581B (en) * | 2012-08-17 | 2014-02-05 | 济南大学 | Preparation method and application of end isocyanate polyurethane |
WO2019188335A1 (en) * | 2018-03-28 | 2019-10-03 | Dic株式会社 | Reactive adhesive agent, laminate film, and packaging body |
JP6650134B1 (en) * | 2018-03-28 | 2020-02-19 | Dic株式会社 | Reactive adhesive, laminated film, and package |
CN108818816A (en) * | 2018-04-24 | 2018-11-16 | 广州精点高分子材料制品有限公司 | A kind of ceramics wood and manufacturing method based on closed NCO |
CN109666180A (en) * | 2018-12-21 | 2019-04-23 | 江苏中信世纪新材料有限公司 | A method of using organotin catalysts solution degradation unsaturated polyester material |
CN113248882A (en) * | 2021-05-25 | 2021-08-13 | 黄山美森新材料科技股份有限公司 | Wear-resistant and impact-resistant plastic-wood material prepared from waste PET (polyethylene terephthalate) bottle and preparation method thereof |
CN113248882B (en) * | 2021-05-25 | 2022-03-18 | 黄山美森新材料科技股份有限公司 | Wear-resistant and impact-resistant plastic-wood material prepared from waste PET (polyethylene terephthalate) bottle and preparation method thereof |
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Application publication date: 20101103 |