CN101967363A - Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof - Google Patents
Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof Download PDFInfo
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- CN101967363A CN101967363A CN2010105076259A CN201010507625A CN101967363A CN 101967363 A CN101967363 A CN 101967363A CN 2010105076259 A CN2010105076259 A CN 2010105076259A CN 201010507625 A CN201010507625 A CN 201010507625A CN 101967363 A CN101967363 A CN 101967363A
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Abstract
The invention relates to isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, a preparation method thereof and use thereof and belongs to the technical field of chemical adhesives. In the invention, PET aqueous emulsion is prepared by using recovered PET, neopentyl glycol, esterification catalyst, heat stabilizer, maleic anhydride and aqueous solution of sodium hydroxide; and when used, the independently packaged PET aqueous emulsion and polymethylene polyisocyanate are mixed at room temperature to obtain the isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive. The adhesive of the invention is used for adhering wood.
Description
Technical field
The present invention relates to a kind of isocyanic ester/PET water miscible liquid tackiness agent and its production and application, belong to the chemical adhesive technical field.
Background technology
Nineteen fifty-three, Du Pont company has realized the suitability for industrialized production of line style thermoplastic polymer polyethylene terephthalate (PET) the earliest.Because PET has unique physics and chemical property, it uses synthon, film and numerous food wrapping material such as the fields such as beverage bottle, mineral water bottle of expanding to rapidly.Add up according to the PET world convention, since 2000, world's PET industry has entered the fast-developing phase of a new round, China PET throughput and output also increase substantially, 2003,2004 and 2005, China PET output has reached 9,730,000 tons, 1,162 ten thousand tons and 1,253 ten thousand tons respectively, and, the growth that keeps of PET output.PET belongs to petrochemicals, and the quick growth of its output has brought the increase of petroleum resources consumptions, therefore, how a large amount of recovery PET are efficiently utilized, and be an important topic of PET recycling economy.
At present, reclaim PET and utilize main employing physical method and chemical process two big classes again.Physical method is with recovery PET heating and melting, extrude grain early again, this method less investment, technology are simple, the useless PET of China reclaims this method that generally adopts, but in the PET heating and melting process, because oxygen brings out side reactions such as degraded and oxidation in water, impurity and the air, cause inevitably that its chemical structure changes, molecular weight and molecular weight, limiting viscosity and physical and mechanical property reduce, so, with the increase of recovered frequency, its reconstituted product quality worse and worse, range of application is more and more narrow, it is discarded finally to contain polymictic PET, and environment has been caused severe contamination.
Reclaiming the PET chemical process and utilize, is to utilize PET macromole generation esterlysis to generate small molecules.Esterlysis mechanism according to PET, reclaim the utilization of PET chemistry and mainly contain alcoholysis method and hydrolysis method, with preparation low molecular monomer compound, as ethylene glycol terephthalate, dimethyl terephthalate (DMT), terephthalic acid two different new esters and terephthalic acid etc., these monomers are used further to synthetic other products.For guaranteeing the quality of derived product, reclaim PET and must clean earlier, the thick product in degraded back need separate, decolours and purify, therefore, and complex process, reaction conditions requires harsh, long reaction time, energy consumption is big, and cost recovery is higher.
China's Forest Resources scarcity, timber lack, and it is significant to substitute timber with preparation wood-based plates such as small diameter grade juggle, brush wood, wood machining residues.China's wood-based plate turnout is very big, and wood adhesive occupies critical role in Wood-based Panel Production.It is reported, the consumption of China's timber industry tackiness agent accounts for more than 60% of whole tackiness agent turnout, its kind and formation and world's most countries are basic identical, mainly based on urea aldehyde (UF) glue, next is phenolic aldehyde (PF) glue and carbamide (MF) glue, with improving constantly of people's quality of life and environmental consciousness, solution contains the pollution problem of aldehyde adhesive and wood-based plate thereof, the development of new formaldehyde-free wood adhesive, with of the pollution of thorough elimination formaldehyde, become the active demand and the challenge of wood adhesive industry development to environment.
Summary of the invention
One of technical assignment of the present invention is in order to remedy the deficiencies in the prior art, provides a kind of to reclaim isocyanic ester/PET water miscible liquid tackiness agent that PET is the main raw material preparation, and this adhesive raw materials cost is low, to bonding wood intensity height.
Two of technical assignment of the present invention provides the preparation method of this isocyanic ester/PET water miscible liquid tackiness agent, its technology of preparing mature and reliable.
Three of technical assignment of the present invention provides the purposes of this isocyanic ester/PET water miscible liquid tackiness agent.
Isocyanic ester of the present invention/PET water miscible liquid tackiness agent is the raw material through chemical reaction preparation by following mass parts:
Reclaim PET 100
Neopentyl glycol 4～7
Esterifying catalyst 0.25～1.0
Thermo-stabilizer 0.5～1.5
Maleic anhydride 5～8
The 1.5%NaOH aqueous solution 160～175
The many phenyl isocyanate 15～30 of polymethine
Advance-go on foot preferably, isocyanic ester/PET water miscible liquid tackiness agent is made by the raw material of following mass parts:
Reclaim PET 100
Neopentyl glycol 5～6
Esterifying catalyst 0.5～0.8
Thermo-stabilizer 0.6～1.0
Maleic anhydride 6～7
The 1.5%NaOH aqueous solution 165～170
The many phenyl isocyanate 20～25 of polymethine
It is one of following that above-described esterifying catalyst is selected from: Mono-n-butyltin, Dibutyltin oxide, tetrabutyl titanate; The use of esterifying catalyst causes under temperature of reaction, and speed of response is accelerated, and the reaction times shortens;
It is one of following that above-described thermo-stabilizer is selected from: trimethyl phosphite 99,2,6 di tert butyl 4 methyl phenol, triphenyl phosphite; The use of thermo-stabilizer avoids in the reaction process temperature too high, and product colour is deepened;
The many phenyl isocyanate of above-described polymethine, viscosity (25 ℃) is 150～250mPa.s, the quality percentage composition of free isocyanate groups (NCO) is 31.5%, and this raw material can be buied in Yantai Wanhua Polyurethane Co., Ltd or in the Chemical market of locality.
The preparation method of the isocyanic ester of the invention described above/PET water miscible liquid tackiness agent, step is as follows:
(1) will reclaim the PET fragmentation, air stream drying, making moisture reduce to mass percent is below 0.5%, solidss such as screening drop, stone, metal;
(2) in reactor, add PET, neopentyl glycol, esterifying catalyst, the thermo-stabilizer that reclaims fragmentation, and turn on agitator, be heated to 265～270 ℃, reaction 180min;
(3) in reactor, add maleic anhydride, react 30min down at 160～180 ℃;
(4) aqueous solution of adding sodium hydroxide in reactor makes resin dispersion get the PET water miscible liquid.
When (5) using, PET oligopolymer water miscible liquid and many phenyl isocyanate of polymethine mixed at room temperature of above-mentioned preparation got isocyanic ester/PET water miscible liquid tackiness agent.
Isocyanic ester of the present invention/PET water miscible liquid adhesive applications is in adhesive bonding of wood, adhesive test:
Carry out with reference to LY/T 1601-2002 " aqueous-based polymers-isocyanate wood adhesive ", the isocyanic ester/PET water miscible liquid tackiness agent that makes is respectively applied for bonding wood gluing plate, the Amount of spread on glued board sandwich layer two sides is 225g/m
2Other gets the veneer of 2 blocks of timber of the same race as dash board and backboard, make the vertical lamination of carrying out of its fiber direction with central layer, earlier in preformer with the 1.0MPa 30min that evenly pressurizes, then, in thermocompressor, pressure with 0.8MPa, even pressurization 3min under 115 ℃ temperature, 1 week of the sheet material room temperature ageing saw part after the compacting is surveyed its Hot water immersion tensile shear strength.Show with of the test of willow Eucalyptus as the examination material, Hot water immersion tensile shear strength average＞1.0MPa, veneer interfacial failure rate proves thus that greater than 96% isocyanic ester of the present invention/PET water miscible liquid tackiness agent has good adhesiveproperties.
Compared with prior art, polymer water miscible liquid tackiness agent of the present invention, its outstanding characteristics are:
(1) will reclaim PET and change the PET water miscible liquid into by chemical reaction
As mentioned above, PET is a polyethylene terephthalate line style thermoplastic polymer, and the present invention has adopted two sections reinforced methods through a large amount of experimental exploring, and will reclaiming PET, directly to change water-dispersible emulsion into by chemical reaction be the PET water miscible liquid; One section reinforced an amount of neopentyl glycol that adds, with the PET polymer degradation is the hydroxyl telechelic polyester oligopolymer of low polymerization degree, two sections reinforced an amount of maleic anhydrides that add, change the hydroxyl telechelic polyester oligopolymer into the terminal carboxyl polyester oligopolymer, introduced the internal emulsification anionic group, make PET pass through chemical reaction, directly change the PET water miscible liquid into, this compares with adding the outer emulsification of tensio-active agent, and the good emulsion stability that makes makes tackiness agent significantly increase adhesive bonding of wood intensity.
(2) used recovery PET to be main raw material
Main raw material of the present invention is for reclaiming PET, this provides new application approach and field for reclaiming the PET resource, and the adhesive raw materials cost that makes is reduced, added value of product increases, for example, the aqueous phenolic aldehyde resin is a timber industry tackiness agent commonly used, but its main raw material phenol price has reached about 15000 yuan/ton at present; In addition, this tackiness agent can be saved and part substitutes the wood adhesive that the petrochemical complex resource prepares.Therefore, the industrialization of this tackiness agent has great importance to the Sustainable development of PET recycling economy and ecotope and wood adhesive.
(3) selected the linking agent of the many phenyl isocyanate of polymethine for use as the PET water miscible liquid
The many phenyl isocyanate of polymethine contain high reactivity free isocyanate group (N=C=O), during hot pressing, this free isocyanate groups can be rapidly and is the active group generation crosslinking reaction of main component with the Mierocrystalline cellulose in the active group in the PET water miscible liquid, moisture and the timber, form and the cementitious adhesive spots of timber, solidify the back and form high bonding strength and water tolerance; In addition, this isocyanic ester belongs to hydrophobic organic compound, and it with the PET water miscible liquid by simply mixing, can be emulsified equably rapidly, with the contact area of remarkable increase and timber, for this reason, this tackiness agent demonstrates outstanding characteristic: high bonding strength, more excellent water tolerance.
(4) because formaldehydeless in this preparation raw material, therefore, this tackiness agent belongs to the environmental protection wood adhesive, can thoroughly solve the puzzlement of traditional aldehyde radical tackiness agent formaldehyde environmental pollution.
(5) this preparation technology is simple, and is easy to operate, and raw materials cost is low, and the industrialization economic and social benefit is remarkable.
Embodiment
Below in conjunction with embodiment the present invention is further described, but protection scope of the present invention not only is confined to embodiment, the change that this field professional does technical solution of the present invention all should belong in protection scope of the present invention.The many phenyl isocyanate of polymethine used among the embodiment are available from Yantai Wanhua Polyurethane Co., Ltd.
Embodiment 1
To reclaim the PET fragmentation, air stream drying, making moisture reduce to mass percent is below 0.5%, solidss such as screening drop, stone, metal; In reactor, add 100kg and reclaim broken PET, neopentyl glycol 5kg, Mono-n-butyltin (esterifying catalyst) 0.5kg, trimethyl phosphite 99 (thermo-stabilizer) 0.6kg, and turn on agitator, be heated to 265～270 ℃, reaction 180min; In reactor, add maleic anhydride 6kg, react 30min down at 160～180 ℃; The adding mass concentration is 1.5% NaOH aqueous solution 165kg in reactor, makes resin dispersion get the PET water miscible liquid.
During use, PET water miscible liquid and many phenyl isocyanate of polymethine 20kg mixed at room temperature of above-mentioned preparation got isocyanic ester/PET water miscible liquid tackiness agent.
Embodiment 2
To reclaim the PET fragmentation, air stream drying, making moisture reduce to mass percent is below 0.5%, solidss such as screening drop, stone, metal; In reactor, add and reclaim broken PET 100kg, neopentyl glycol 6kg, Dibutyltin oxide (esterifying catalyst) 0.8kg, 2,6-di-tert-butyl-4-methy phenol (thermo-stabilizer) 0.9kg, and turn on agitator, be heated to 265～270 ℃, reaction 180min; In reactor, add maleic anhydride 7kg, react 30min down at 160～180 ℃; The adding mass concentration is 1.5% NaOH aqueous solution 170kg in reactor, makes resin dispersion get the PET water miscible liquid.
During use, PET water miscible liquid and many phenyl isocyanate of polymethine 25kg mixed at room temperature of above-mentioned preparation got isocyanic ester/PET water miscible liquid tackiness agent.
Embodiment 3
To reclaim the PET fragmentation, air stream drying, making moisture reduce to mass percent is below 0.5%, solidss such as screening drop, stone, metal; In reactor, add and reclaim broken PET 100kg, neopentyl glycol 5.5kg, tetrabutyl titanate (esterifying catalyst) 0.6kg, triphenyl phosphite (thermo-stabilizer) 0.75kg, and turn on agitator, be heated to 265～270 ℃, reaction 180min; In reactor, add maleic anhydride 6.5kg, react 30min down at 160～180 ℃; The adding mass concentration is 1.5% NaOH aqueous solution 168kg in reactor, makes resin dispersion get the PET water miscible liquid.
During use, PET water miscible liquid and many phenyl isocyanate of polymethine 23kg mixed at room temperature of above-mentioned preparation got isocyanic ester/PET water miscible liquid tackiness agent.
Claims (5)
1. isocyanic ester/PET water miscible liquid tackiness agent is characterized in that being got by the feedstock production of following mass parts:
Reclaim PET 100
Neopentyl glycol 4～7
Esterifying catalyst 0.25～1.0
Thermo-stabilizer 0.5～1.5
Maleic anhydride 5～8
The 1.5%NaOH aqueous solution 160～175
The many phenyl isocyanate 15～30 of polymethine
It is one of following that described esterifying catalyst is selected from: Mono-n-butyltin, Dibutyltin oxide, tetrabutyl titanate, described thermo-stabilizer are selected from one of following: trimethyl phosphite 99,2,6 di tert butyl 4 methyl phenol, triphenyl phosphite.
2. isocyanic ester/PET water miscible liquid tackiness agent is characterized in that being got by the feedstock production of following mass parts:
Reclaim PET 100
Neopentyl glycol 5～6
Esterifying catalyst 0.5～0.8
Thermo-stabilizer 0.6～1.0
Maleic anhydride 6～7
1.5% the NaOH aqueous solution 165～170
The many phenyl isocyanate 20～25 of polymethine
3. the preparation method of the described isocyanic ester of claim 1/PET water miscible liquid tackiness agent, step is as follows:
(1) will reclaim the PET fragmentation, air stream drying, making moisture reduce to mass percent is below 0.5%, solidss such as screening drop, stone, metal;
(2) in reactor, add PET, neopentyl glycol, esterifying catalyst, the thermo-stabilizer that reclaims fragmentation, and turn on agitator, be heated to 265～270 ℃, reaction 180min;
(3) in reactor, add maleic anhydride, react 30min down at 160～180 ℃;
(4) aqueous solution of adding sodium hydroxide in reactor makes resin dispersion get the PET water miscible liquid.
When (5) using, PET water miscible liquid and many phenyl isocyanate of polymethine mixed at room temperature of packing get isocyanic ester/PET water miscible liquid tackiness agent separately.
4. the application of the described isocyanic ester of claim 1/PET water miscible liquid tackiness agent is used for adhesive bonding of wood.
5. the application of isocyanic ester as claimed in claim 1/PET water miscible liquid tackiness agent, the Amount of spread on glued board sandwich layer two sides is 225g/m
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201010507625A CN101967363B (en) | 2010-10-15 | 2010-10-15 | Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof |
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| CN201010507625A CN101967363B (en) | 2010-10-15 | 2010-10-15 | Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof |
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| CN101967363B CN101967363B (en) | 2012-10-03 |
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Cited By (5)
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|---|---|---|---|---|
| CN102558531A (en) * | 2011-12-31 | 2012-07-11 | 济南大学 | Amine polyester-polyether and preparation method and application thereof |
| CN102775575A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of double-component polyurethane |
| CN102775581A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of novel end isocyanate polyurethane |
| CN103724617A (en) * | 2013-12-30 | 2014-04-16 | 济南大学 | Preparation method and application of carboxyl-terminated polyester-amide-ether aqueous emulsion |
| CN105670551A (en) * | 2016-04-14 | 2016-06-15 | 久盛地板有限公司 | Recombined wood board adopting polyimide modified polyurethane adhesive and preparation method of polyimide modified polyurethane adhesive |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558531A (en) * | 2011-12-31 | 2012-07-11 | 济南大学 | Amine polyester-polyether and preparation method and application thereof |
| CN102775575A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of double-component polyurethane |
| CN102775581A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Preparation method and application of novel end isocyanate 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 |
| CN103724617A (en) * | 2013-12-30 | 2014-04-16 | 济南大学 | Preparation method and application of carboxyl-terminated polyester-amide-ether aqueous emulsion |
| CN103724617B (en) * | 2013-12-30 | 2016-01-20 | 济南大学 | A kind of preparation method and application of terminal carboxyl polyester-acid amides-ether water miscible liquid |
| CN105670551A (en) * | 2016-04-14 | 2016-06-15 | 久盛地板有限公司 | Recombined wood board adopting polyimide modified polyurethane adhesive and preparation method of polyimide modified polyurethane adhesive |
| CN105670551B (en) * | 2016-04-14 | 2018-11-30 | 久盛地板有限公司 | Using the reconstructed and preparation method thereof of polyimide modified adhesive for polyurethane |
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