CN101948670A - Preparation method and application of water-based polymer adhesive - Google Patents
Preparation method and application of water-based polymer adhesive Download PDFInfo
- Publication number
- CN101948670A CN101948670A CN 201010507669 CN201010507669A CN101948670A CN 101948670 A CN101948670 A CN 101948670A CN 201010507669 CN201010507669 CN 201010507669 CN 201010507669 A CN201010507669 A CN 201010507669A CN 101948670 A CN101948670 A CN 101948670A
- Authority
- CN
- China
- Prior art keywords
- pet
- aqueous
- sizing agent
- based polymers
- reactor
- 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.)
- Granted
Links
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention relates to a preparation method and application of a water-based polymer adhesive, and belongs to the technical field of chemical adhesives. PET aqueous polymer emulsion is prepared from recycled polyethylene terephthalate (PET), ethanolamine, an esterification catalyst, a heat stabilizer, phthalic anhydride and aqueous solution of sodium hydroxide; and when used, the PET aqueous polymer emulsion which is packaged independently is mixed with diphenylmethane-4,4'-diisocyanate at room temperature to obtain the water-based polymer adhesive. The water-based polymer adhesive is used for adhering wood plywood.
Description
Technical field
The present invention relates to a kind of aqueous-based polymers sizing agent preparation method and application, be specifically related to a kind of aqueous-based polymers timber sizing agent preparation method and application, belong to chemical sizing agent technical field.
Background technology
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 the timber sizing agent occupies critical role in Wood-based Panel Production.It is reported that the consumption of China's timber industry sizing agent accounts for more than 60% of whole sizing agent turnout.At present, the sizing agent that timber industry is used mainly is " three urea formaldehydes ", be urea-formaldehyde resin, resol and melamine formaldehyde resin glue, wherein urea-formaldehyde resin is cheap, its market share is up to more than 40%, but the wood-based plate of urea-formaldehyde resin gluing in use produces formaldehyde, and this causes very big hidden danger to human health.With improving constantly of people's quality of life and environmental consciousness, solution contains the pollution problem of aldehyde sizing agent and wood-based plate thereof, development of new formaldehyde-free wood sizing agent is thoroughly eliminated the pollution of formaldehyde to environment, becomes the active demand and the challenge of timber sizing agent industry development.
Application number is the patent of invention of CN200910031280.1, discloses a kind of preparation method of aqueous polyurethane sizing agent of wood working; Its preparation is divided into three phases, and the fs by progressively polymerization and radical polymerization, generates modified polyurethane prepolymer by oligomer polyol, hydrophilic monomer, isocyanic ester, modified monomer; Subordinate phase is disperseed in water with salify post-modification base polyurethane prepolymer for use as in being; Phase III forms aqueous polyurethane emulsion after adding chainextender; Because highly active isocyanate group in this sizing agent (N=C=O) step-reaction polymerization has taken place, so, when being applied to the timber gluing, be difficult to the bonding action that reaches more excellent.Application number is the patent of invention of CN200810051264.4, the preparation method of another kind of timber sizing agent is disclosed, this sizing agent is to be main raw material with starch and polyvinyl alcohol, by to after the pre-treatment such as starch pasting and oxidation with the polyvinyl alcohol graft copolymerized sizing agent host that makes, adding aqueous SBS emulsion or melamine formaldehyde resin to it again carries out modification and makes, because this sizing agent has used starch to be one of main raw material, so its industrialization may exert an influence to grain security.
Polyethylene terephthalate (PET) has unique physics and chemical property, and its application comprises synthon, film and numerous food wrapping material such as fields such as beverage bottle, mineral water bottle.Add up according to the PET world convention, since 2000, world's PET industry has entered the fast-developing phase of a new round, and 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, therefore, to reclaim the timber sizing agent that PET is prepared into high performance-price ratio, the development of PET recycling economy and timber industry sizing agent will all be had great importance.
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 the preparation method that PET is the aqueous-based polymers sizing agent of main raw material preparation, and this sizing agent raw materials cost is low, the technology of preparing mature and reliable.
Two of technical assignment of the present invention provides the application of this aqueous-based polymers sizing agent, and this sizing agent is used for the timber gluing, to timber bonding action height.
Aqueous-based polymers sizing agent preparation method of the present invention, 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) PET, thanomin 5～7kg, esterifying catalyst 0.5～0.8kg, the thermo-stabilizer 0.6～1.0kg of the recovery fragmentation of adding 100kg in reactor, and turn on agitator are heated to 265～270 ℃, reaction 30min;
(3) in reactor, add phthalic anhydride 6～10kg, react 30min down at 160～180 ℃;
(4) the aqueous solution 165～170kg of adding ammonia in reactor, transferring pH is 8.0, makes resin dispersion get PET aqueous-based polymers emulsion.
When (5) using, with the PET aqueous-based polymers emulsion of preparation and ditan-4,4 '-vulcabond gets the aqueous-based polymers sizing agent by mass ratio 100: 3～10 mixed at room temperature.
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;
Above-described ditan-4,4 '-vulcabond, viscosity (25 ℃) is 150～250mPa.s, and the quality percentage composition of free isocyanate groups (NCO) is 30.2～32.0%, and this raw material can be buied in Yantai Wanhua Polyurethane Co., Ltd or in the Chemical market of locality.
Aqueous-based polymers sizing agent of the present invention is applied to the gluing of wood gluing plate, the gluing test:
Carry out with reference to LY/T 1601-2002 " aqueous-based polymers-isocyanate wood sizing agent ", a veneer test piece two sides is coated with the aqueous-based polymers sizing agent as central layer, Amount of spread is 200g/m
2Other gets 2 veneer test pieces as dash board and backboard, make the vertical lamination of carrying out of its fiber direction and central layer become test specimen, earlier with the even precompressed 30min of the pressure of 1.0MPa, then, in thermocompressor, pressure with 0.8MPa, in 115 ℃ of 3min that evenly pressurize, 1 week of the sheet material room temperature ageing saw part after the compacting serves as that examination material test-results shows with the willow Eucalyptus, the Hot water immersion tensile shear strength average＞1.0MPa of test specimen, veneer substrate interface destructive rate proves thus that greater than 96% isocyanic ester of the present invention/PET water miscible liquid sizing agent has good gluing performance.
Compared with prior art, aqueous-based polymers sizing agent of the present invention, its outstanding characteristics are:
(1) will reclaim PET and change PET aqueous-based polymers emulsion 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, will reclaim PET and directly change PET waterborne polymeric sizing agent into by chemical reaction; One section reinforced an amount of thanomin that adds, with the PET polymer degradation is the hydroxyl telechelic polyester-oligoamide of low polymerization degree, two sections reinforced an amount of phthalic anhydrides that add, change hydroxyl telechelic polyester-oligoamide into terminal carboxyl polyester-oligoamide, introduce the internal emulsification anionic group, made PET pass through chemical reaction, directly changed PET aqueous-based polymers emulsion into, this compares with adding the outer emulsification of tensio-active agent, and sizing agent is increased greatly to the bonding action of timber.
(2) used recovery PET to be main raw material
This invention main raw material is for reclaiming PET, and this provides new Application Areas and approach for reclaiming the PET resource, and the sizing agent raw materials cost that makes is reduced, and added value of product increases; In addition, this sizing agent also can be saved and part substitutes other timber sizing agents that the petrochemical complex resource prepares, and therefore, the industrialization of this sizing agent has great importance to the Sustainable development of PET recycling economy and ecotope and timber sizing agent.
(3) selected for use ditan-4,4 '-vulcabond is as the linking agent of aqueous-based polymers emulsion
Ditan-4,4 '-vulcabond contains high reactivity free isocyanate group (N=C=O), during hot pressing, this isocyanic ester free isocyanate group can be rapidly and is the active group generation crosslinking reaction of main component with the Mierocrystalline cellulose in active group, moisture and the timber in the PET aqueous-based polymers emulsion, form and the cementitious gluing point 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 and the simple mechanically mixing of PET water miscible liquid, can be emulsified equably rapidly, the contact area of remarkable increase and timber, for this reason, this sizing agent demonstrates distinctive characteristic: high bonding action, more excellent water tolerance.
(4) because this prepares formaldehydeless and other organic solvents in raw material,, can thoroughly solve the puzzlement of traditional aldehyde radical sizing agent environmental pollution so this sizing agent belongs to environmental protection timber sizing agent.
(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.Used ditan-4,4 among the embodiment '-vulcabond is available from Yantai Wanhua Polyurethane Co., Ltd, and other raw materials are commercially available technical grade.
Embodiment 1
To reclaim the PET fragmentation, air stream drying makes moisture reduce to mass percent below 0.5%, solidss such as screening drop, stone, metal; In reactor, add 100kg and reclaim broken PET, thanomin 5kg, esterifying catalyst Mono-n-butyltin 0.5kg, thermo-stabilizer trimethyl phosphite 99 0.6kg, and turn on agitator, be heated to 265～270 ℃, reaction 30min; In reactor, add phthalic anhydride 6kg, react 30min down at 160～180 ℃; Add the aqueous solution 165kg of ammonia in reactor, transferring pH is 8.0, makes resin dispersion get the PET aqueous polymer emulsion.
During use, with the PET aqueous polymer emulsion of preparation and ditan-4,4 '-vulcabond gets aqueous-based polymers timber sizing agent by 100: 5 mixed at room temperature of mass ratio.
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; PET, the thanomin 7kg, esterifying catalyst Dibutyltin oxide 0.8kg, the thermo-stabilizer 2,6 di tert butyl 4 methyl phenol 1.0kg that add the recovery fragmentation of 100kg in reactor, and turn on agitator are heated to 265～270 ℃, reaction 30min; In reactor, add phthalic anhydride 10kg, react 30min down at 160～180 ℃; Add the aqueous solution 170kg of ammonia in reactor, transferring pH is 8.0, makes resin dispersion get the PET aqueous polymer emulsion.
During use, with the PET aqueous polymer emulsion of preparation and ditan-4,4 '-vulcabond gets aqueous-based polymers timber sizing agent by 100: 8 mixed at room temperature of mass ratio.
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; PET, the thanomin 6kg, esterifying catalyst tetrabutyl titanate 0.6kg, the thermo-stabilizer triphenyl phosphite 0.7kg that add the recovery fragmentation of 100kg in reactor, and turn on agitator are heated to 265～270 ℃, reaction 30min; In reactor, add phthalic anhydride 8kg, react 30min down at 160～180 ℃; Add the aqueous solution 168kg of ammonia in reactor, transferring pH is 8.0, makes resin dispersion get the PET aqueous polymer emulsion.
During use, with the PET aqueous polymer emulsion of preparation and ditan-4,4 '-vulcabond gets aqueous-based polymers timber sizing agent by 100: 6 mixed at room temperature of mass ratio.
Claims (3)
1. aqueous-based polymers sizing agent preparation method is characterized in that:
(1) will reclaim the PET fragmentation, air stream drying makes moisture reduce to mass percent below 0.5%, solidss such as screening drop, stone, metal;
(2) in reactor, add 100kg and reclaim broken PET, thanomin 5～7kg, esterifying catalyst 0.5～0.8kg, thermo-stabilizer 0.6～1.0kg, and turn on agitator, be heated to 265～270 ℃, reacted 30 minutes;
(3) in reactor, add phthalic anhydride 6～10kg, reacted 30 minutes down at 160～180 ℃;
(4) the aqueous solution 165～170kg of adding ammonia in reactor, transferring pH is 8.0, makes resin dispersion get the PET aqueous polymer emulsion;
When (5) using, with PET aqueous polymer emulsion and ditan-4,4 '-vulcabond gets the aqueous-based polymers sizing agent by mass ratio 100: 3～10 mixed at room temperature;
It is one of following that above-described esterifying catalyst is selected from: Mono-n-butyltin, Dibutyltin oxide, tetrabutyl titanate;
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.
2. the application of the described aqueous-based polymers sizing agent of claim 1 is used for the gluing of timber.
3. the application of the described aqueous-based polymers sizing agent of claim 1 is 200g/m to the Amount of spread of wood gluing plate
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105076691A CN101948670B (en) | 2010-10-15 | 2010-10-15 | Preparation method and application of water-based polymer adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105076691A CN101948670B (en) | 2010-10-15 | 2010-10-15 | Preparation method and application of water-based polymer adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101948670A true CN101948670A (en) | 2011-01-19 |
| CN101948670B CN101948670B (en) | 2012-07-04 |
Family
ID=43452302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105076691A Expired - Fee Related CN101948670B (en) | 2010-10-15 | 2010-10-15 | Preparation method and application of water-based polymer adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101948670B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769289A (en) * | 2012-01-21 | 2014-05-07 | 金安国纪科技股份有限公司 | Reutilization method of prepreg edge trimming material |
| CN104725260A (en) * | 2015-01-22 | 2015-06-24 | 漳州亚邦化学有限公司 | Method for degrading PET and synthesizing unsaturated polyester resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070406A (en) * | 2005-09-05 | 2007-03-22 | Oshika:Kk | Water-based adhesive composition |
| CN101798495A (en) * | 2009-02-10 | 2010-08-11 | 上海诺科化工新材料有限公司 | Method for synthesizing water-solubility or water-dispersity adhesives by recycling polyester waste materials |
-
2010
- 2010-10-15 CN CN2010105076691A patent/CN101948670B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070406A (en) * | 2005-09-05 | 2007-03-22 | Oshika:Kk | Water-based adhesive composition |
| CN101798495A (en) * | 2009-02-10 | 2010-08-11 | 上海诺科化工新材料有限公司 | Method for synthesizing water-solubility or water-dispersity adhesives by recycling polyester waste materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769289A (en) * | 2012-01-21 | 2014-05-07 | 金安国纪科技股份有限公司 | Reutilization method of prepreg edge trimming material |
| CN103769289B (en) * | 2012-01-21 | 2015-10-07 | 金安国纪科技股份有限公司 | A kind of reuse method of prepreg cutting edge material |
| CN104725260A (en) * | 2015-01-22 | 2015-06-24 | 漳州亚邦化学有限公司 | Method for degrading PET and synthesizing unsaturated polyester resin |
| CN104725260B (en) * | 2015-01-22 | 2017-08-29 | 漳州亚邦化学有限公司 | The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101948670B (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101948669B (en) | Preparation method and use of aqueous polymer/isocyanate adhesive | |
| AU2011285710B2 (en) | Tackifiers for composite articles | |
| CN1264942C (en) | Water-thinned isocyanate adhesive with corn starch as main material and its prepn process | |
| CN101892023B (en) | Aldehyde-free adhesive and preparation method thereof | |
| CN102086367B (en) | Plate alignment adhesive for surface plate lamination of engineered wood flooring and preparation method thereof | |
| CN1687279A (en) | Method for preparing starch glue for lumber | |
| CN101805568A (en) | Bio oil-starch adhesive and preparation method thereof | |
| CN110079270A (en) | A kind of fibre modification soybean protein base adhesive of wood-based plate and preparation method thereof | |
| CN101967363B (en) | Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof | |
| CN113355050A (en) | Biological aldehyde-free glue, biological composite material and preparation method thereof | |
| Wang et al. | Enhanced performance of urea–glyoxal polymer with oxidized cassava starch as wood adhesive | |
| CN101948670B (en) | Preparation method and application of water-based polymer adhesive | |
| CN101979423B (en) | Water-based polymer-polyurethane prepolymer preparation method and application | |
| Zeng et al. | Preparation a novel high performance glucose-based wood adhesive with hyperbranched cross-linked network by air oxidation | |
| CN103320082B (en) | Plant-based polyester polyol adhesive, and preparation method and application thereof | |
| CN111234132B (en) | Water-based epoxy resin cross-linking agent, modified protein adhesive and application | |
| CN103320081B (en) | High-molecular composite adhesive, and preparation method and application thereof | |
| CN102532447A (en) | Urea resin prepared by multilevel segmentation control, and continuous synthesis method | |
| CN109181610A (en) | It is a kind of for bonding wood materials low cost without the agent of aldehyde environmental-friendly adhesion and preparation method | |
| CN101831256B (en) | Biomass wood adhesive and preparation method thereof | |
| CN104312502A (en) | Novel starch-based quebracho tannin extract aldehyde-free wood adhesive and preparation method thereof | |
| CN113510819A (en) | Aldehyde-free all-plant fiber density board based on nanocellulose and preparation method thereof | |
| JPS60206883A (en) | Production of adhesive | |
| CN108949097B (en) | Industrial gelatin-enclosed water-based polyurethane adhesive composition and construction method thereof | |
| CN101979422B (en) | Method for preparing environmentally-friendly macromoleclar polymer and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20121015 |