CN102604021A - Method for synthesizing urea-formaldehyde resin containing micro free formaldehyde for E0-level artificial boards - Google Patents
Method for synthesizing urea-formaldehyde resin containing micro free formaldehyde for E0-level artificial boards Download PDFInfo
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- CN102604021A CN102604021A CN2012100370762A CN201210037076A CN102604021A CN 102604021 A CN102604021 A CN 102604021A CN 2012100370762 A CN2012100370762 A CN 2012100370762A CN 201210037076 A CN201210037076 A CN 201210037076A CN 102604021 A CN102604021 A CN 102604021A
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- CN
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- Prior art keywords
- urea
- formaldehyde
- formaldehyde resin
- wood
- resin
- 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.)
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 20
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 title abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000002023 wood Substances 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- GMIMEXBGMYDQTO-UHFFFAOYSA-N C=O.C=O.NC(N)=O Chemical compound C=O.C=O.NC(N)=O GMIMEXBGMYDQTO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000003292 glue Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- -1 methylol reactive group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
本发明E0级人造板用微游离甲醛脲醛树脂合成方法，涉及脲醛树脂胶技术领域。以尿素、37%甲醛水溶液为原料，采用“弱碱-弱酸-弱碱”三级pH拟稳态控制聚合反应工艺生产脲醛树脂产品。游离甲醛含量小于0.05%，使用该树脂制备的人造板制品具有甲醛释放量≤0.1mg/L，满足GB/T14732-2006，对用户使用无危害，同时该树脂满足了其在含水率、胶合强度等方面的要求，达到E0级水平。The invention discloses a method for synthesizing micro-free formaldehyde urea-formaldehyde resin for E0 grade wood-based panels, and relates to the technical field of urea-formaldehyde resin glue. Using urea and 37% formaldehyde aqueous solution as raw materials, urea-formaldehyde resin products are produced by adopting "weak base-weak acid-weak base" three-stage pH quasi-steady-state control polymerization reaction process. The free formaldehyde content is less than 0.05%. The wood-based panel products prepared by using this resin have a formaldehyde emission of ≤0.1mg/L, which meets GB/T14732-2006 and is not harmful to users. At the same time, the resin meets its moisture content and bonding strength. And other requirements, to reach the E0 level.
Description
Technical field
The present invention relates to E0 level wood-based plate with little free formaldehyde urea-formaldehyde resin compound method, relate to the urea-formaldehyde resin adhesive technical field.Can be used for forming the mechanicals that ultralow free formaldehyde discharges.Advantages such as the urea-formaldehyde resin adhesive that this method is produced has bonding strength height, quick solidifying, processing property is good, with low cost, raw material sources are abundant; In wood working, covering with paint industry, paper bonding, toughened paint, especially wood veneer, shaving board, the production of fibre board use tackiness agent, be widely used.
Background technology
Urea-formaldehyde resin has higher bonding strength, good cold-resistant water-based ability, medium hot water resistance ability, solidifies rapidly, and the glue-line after the curing is of light color, can not pollute by the plate face of agglutinent, and is good with the compatibility of water, is prone to modulate suitable viscosity and concentration; In addition, urea-formaldehyde resin also has advantages such as initial viscosity is big, processing property is good, production technique is simple, makes it be widely used aspect the preparation wood-based plate.
Present main method of producing low formaldehyde emissions wood-based plate both at home and abroad is: start with from the synthesizing formula and the technology of urea-formaldehyde resin adhesive, through regulating proportioning raw materials, methods such as change reaction conditions reduce the free formaldehyde content in the urea-formaldehyde resin as far as possible; Prepare at sheet material and to add methanal trapping agent in the process, to catch the formaldehyde that constantly discharges in the wood-based plate use; Wood-based plate to preparing carries out aftertreatment etc.But these methods all do not solve the long-term release problem that causes formaldehyde in the wood-based plate use because of the resin structure factor.Particularly the adding of a large amount of properties-correcting agent has improved the cost of product greatly, is difficult to carry out marketing.
Because the constitutional features of urea-formaldehyde resin itself contains methylol, possess hydrophilic property, facile hydrolysis under acidic conditions in the molecule; Methylol in the urea-formaldehyde resin molecule and-NH
2Be prone to crosslinkedly, so urea-formaldehyde resin has and solidifies internal stress that the back produces and make glue-line become fragile, be prone to problems such as be full of cracks, water tolerance and loss of properties on aging and easy gel, poor stability.Particularly low mol ratio urea-formaldehyde glue is owing to exist free-NH
2Many, crosslinkable groups-CH
2The OH number is few, causes bonding strength low, and water resistance, plywood production technology operability difference etc. are the multimass problem more.
The major cause of urea-formaldehyde resin adhesive product release formaldehyde in manufacturing and use has the following aspects: 1. the addition condensation reaction of urea and formaldehyde is a reversible; Equilibrium principle according to reversible reaction; Though can improve the formaldehyde transformation efficiency through changing reaction conditions, always some formaldehyde is because of can not complete reaction remaining in the resin; 2. when the synthetic urea-formaldehyde resin of urea and formaldehyde, might form unstable groups such as ehter bond, semi-acetal, they decompose in wood-based plate hot pressing or use and discharge formaldehyde; 3. in resin curing process, be prone between the methylol reactive group form unsettled ehter bond, in the wood-based plate use, be prone to decomposition and discharge formaldehyde (owing to the existence of the protonated formaldehyde molecule of part; Around colloidal particle, form the two particle layers of absorption; The stability of resin is strengthened, in case after adding solidifying agent, resin is under electrolytical effect; The granule for absorbing layer is destroyed, thereby discharges formaldehyde); 4. wood-based plate and goods thereof in use because the effect of moisture content and light makes resin aging, constantly decompose generation formaldehyde.
At present, a lot of in this environmental protection of preparation, practical Study on urea-formaldehyde, mainly contain following certain methods: the amount of substance that 1. reduces urea (U) PARA FORMALDEHYDE PRILLS(91,95) (F) is than (be called for short F/U than) (USP-4968772, USP-4968773, CN-1294618); 2. develop various formaldehyde-trapping agents and modifier (Chinese patent CN-103438, CN-1262301, CN-1092632); 3. vacuum hydro-extraction extracting free formaldehyde, this method have aldehyde-containing sewage to discharge, and cost of equipment is high; 4. UF resinoid bond goods are carried out aftertreatment with ammonia or urea soln; PH value, temperature of reaction and the reaction times of 5. strict control urea-formaldehyde glue production process; 7. optimize plywood hot-pressing technology, and the water cut that suitably improves slab.
Summary of the invention
The purpose of this invention is to provide a kind of E0 level wood-based plate with little free formaldehyde urea-formaldehyde resin compound method, have both high-level efficiency, low cost, the release of ultralow free formaldehyde and the stable characteristics of product performance.The urea-formaldehyde resin of producing contains the free formaldehyde less than 0.05%, has the premium properties of low toxicity, minimum discharge, has eliminated the environmental pollution of wood-based plate in use.
Another object of the present invention provides a kind of environmental protection urea-formaldehyde resin adhesive product; Be applicable to the use in wood-based plate industry and furniture decoration field; Use the artifical plate product of this resins to have burst size of methanal≤0.1mg/L, satisfy GB/T14732-2006, the user is used does not have harm; This resin has satisfied its requirement at aspects such as water ratio, bonding strengths simultaneously, reaches E0 level level.
A kind of E0 level wood-based plate carries out according to following step with little free formaldehyde urea-formaldehyde resin compound method: formalin is once added in the reaction kettle, and the sodium hydroxide solution with 20% is transferred pH to 6.5 ~ 7.0; Be heated to 50 ~ 53 ℃; Add first urea, be warming up to 85 ~ 88 ℃, insulation 15min; Transfer pH to 3.0 ~ 3.5, polymerization under 65 ~ 75 ℃ temperature condition; Transfer pH to 6.5 ~ 7.0, add second batch of urea, be acidified to pH4.0 ~ 4.4, stir 15min under the equality of temperature with formic acid; , add the 3rd batch of urea, about 65 ~ 75 ℃, stir 5min; Transfer pH to 4.0 ~ 4.4 with formic acid then, stir 15min in 65 ~ 75 ℃; Transfer pH to 6.5 ~ 7.0 with ammoniacal liquor,, reduce to the room temperature discharging in the vacuum distilling dehydration.
Wherein urea and formaldehyde mole ratio 1～1.4:1, it is 3:2:1 that three batches of urea add mass ratioes.
It is characterized in that the formalin mass concentration is 37%.
The present invention has the following advantages:
1. adopt weak base-weak acid-weak base quasi-stable state synthesis technique, synthetic urea-formaldehyde resin in three grades of series connection substep controlling reactor makes its free formaldehyde content≤0.05%.
2. through formaldehyde and urea " adding, multi-spot segmentation in batches ", effectively regulate each stage feeding quantity of condensation reaction, pH value and temperature controlling system; Promote the formation of " build " organic molecule from microcosmic; Improve the polycondensation degree, reduce the content of methylol, methylene ether, hemiformal, minimizing maybe be because of the formaldehyde of changes in environmental conditions generation.
The urea-formaldehyde resin product quality indicator of 3, producing satisfies the requirement of standard GB/T 14732-2006, and reaches the imported product level; Product free formaldehyde content≤0.05% (wt.), burst size of methanal≤0.1mg/L, the burst size of methanal value of limiting the quantity of after the product application reaches the technical requirements of E0 level wood-based plate.
Embodiment
Embodiment 1
Formalin 100g is once added in the reaction kettle, and the sodium hydroxide solution with 20% is transferred pH to 6.5 ~ 7.0, is heated to 50 ~ 53 ℃, adds first urea 60g, is warming up to 85 ~ 88 ℃, insulation 15min; Transfer pH to 3.0 ~ 3.5, polymerization under 65 ~ 75 ℃ temperature condition; Transfer pH to 6.5 ~ 7.0, add second crowd of urea 40g, be acidified to pH4.0 ~ 4.4, stir 15min under the equality of temperature with formic acid; , add the 3rd crowd of urea 20g, about 65 ~ 75 ℃, stir 5min; Transfer pH to 4.0 ~ 4.4 with formic acid then, stir 15min in 65 ~ 75 ℃; Transfer pH to 6.5 ~ 7.0 with ammoniacal liquor,, reduce to the room temperature discharging, obtain the product free formaldehyde content less than 0.05% environment protection type urea formaldehyde resin adhesive in the vacuum distilling dehydration.
The urea-formaldehyde resin of being produced has following typical characteristics:
Solid content 62%
Viscosity 280 mPas
PH value 7.8
Proportion 1.25g/ml
Free formaldehyde 0.05%
80 days shelf liveves
Embodiment 2
Urea-formaldehyde resin among the embodiment 1 is coated in the cemented surface of wood-based plate; Amount of spread is 280～300g/m2 (single face), and two parallel rift grains of examination material adopt 0.78～1.18MPa (pressure of 8～12kgf/cm2) to lumping together; Behind the following precompressed 0.5～1.0h of room temperature (being not less than 20 ℃); In temperature is hot pressing 5min under 100～110 ℃ of conditions, and moulding makes wood-based plate.Its salient features is following.
Water ratio 8%
Free formaldehyde release 0.1mg/L
Bonding strength 0.8MPa
Use production urea-formaldehyde resin product quality indicator provided by the invention to satisfy the requirement of standard GB/T 14732-2006, and reach the imported product level; Product free formaldehyde content≤0.05% (wt.), the burst size of methanal value of limiting the quantity of after the product application reaches the technical requirements of E0 level wood-based plate.
Claims (3)
1. an E0 level wood-based plate is with little free formaldehyde urea-formaldehyde resin compound method; It is characterized in that carrying out: once add formalin in the reaction kettle according to following step; Sodium hydroxide solution with 20% is transferred pH to 6.5 ~ 7.0, is heated to 50 ~ 53 ℃, adds first urea; Be warming up to 85 ~ 88 ℃, insulation 15min; Transfer pH to 3.0 ~ 3.5, polymerization under 65 ~ 75 ℃ temperature condition; Transfer pH to 6.5 ~ 7.0, add second batch of urea, be acidified to pH4.0 ~ 4.4, stir 15min under the equality of temperature with formic acid; , add the 3rd batch of urea, about 65 ~ 75 ℃, stir 5min; Transfer pH to 4.0 ~ 4.4 with formic acid then, stir 15min in 65 ~ 75 ℃; Transfer pH to 6.5 ~ 7.0 with ammoniacal liquor,, reduce to the room temperature discharging in the vacuum distilling dehydration.
2. a kind of E0 level wood-based plate according to claim 1 is characterized in that wherein urea and formaldehyde mole ratio 1～1.4:1 with little free formaldehyde urea-formaldehyde resin compound method, and it is 3:2:1 that three batches of urea add mass ratio.
3. a kind of E0 level wood-based plate according to claim 1 is characterized in that with little free formaldehyde urea-formaldehyde resin compound method wherein the formalin mass concentration is 37%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210037076 CN102604021B (en) | 2012-02-20 | 2012-02-20 | Method for synthesizing urea-formaldehyde resin containing micro free formaldehyde for E0-level artificial boards |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210037076 CN102604021B (en) | 2012-02-20 | 2012-02-20 | Method for synthesizing urea-formaldehyde resin containing micro free formaldehyde for E0-level artificial boards |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604021A true CN102604021A (en) | 2012-07-25 |
| CN102604021B CN102604021B (en) | 2013-12-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210037076 Expired - Fee Related CN102604021B (en) | 2012-02-20 | 2012-02-20 | Method for synthesizing urea-formaldehyde resin containing micro free formaldehyde for E0-level artificial boards |
Country Status (1)
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|---|---|
| CN (1) | CN102604021B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059583A (en) * | 2014-06-09 | 2014-09-24 | 杨超 | Preparation method of special urea-formaldehyde resin adhesive for artificial boards |
| CN104194694A (en) * | 2014-08-14 | 2014-12-10 | 广东五联木业集团有限公司 | Preparation method of environment-friendly glue for shaving board |
| CN104388008A (en) * | 2014-10-27 | 2015-03-04 | 深圳市永丽威胶粘科技有限公司 | Environment-friendly no-pollution strapping paper |
| CN104448178A (en) * | 2013-09-24 | 2015-03-25 | 南京理工大学 | Urea-formaldehyde (UF) resin and method for removing boric acid in boron-containing waste liquor by using same |
| CN105018012A (en) * | 2015-07-28 | 2015-11-04 | 湖北鸿连实业有限公司 | Low-formaldehyde-content glue |
| CN105017498A (en) * | 2015-07-03 | 2015-11-04 | 昆明新飞林人造板有限公司 | Preparation method of urea formaldehyde resin for E0 grade particleboards |
| CN105778839A (en) * | 2016-04-21 | 2016-07-20 | 广西农垦糖业集团良圻制糖有限公司 | Urea-formaldehyde resin glue for bagasse particleboard and preparation method thereof |
| CN109235120A (en) * | 2018-10-10 | 2019-01-18 | 广州市顺誉装饰材料有限公司 | A kind of environment protecting paper and preparation method thereof |
| CN109485811A (en) * | 2018-10-10 | 2019-03-19 | 中南林业科技大学 | A kind of method that discarded Lauxite degradation recycles |
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|---|---|---|---|---|
| CN101519483A (en) * | 2008-04-30 | 2009-09-02 | 北京化工大学 | Novel environment-friendly urea-formaldehyde resin and preparation method thereof |
| CN101585964A (en) * | 2009-04-20 | 2009-11-25 | 永港伟方（北京）科技股份有限公司 | Urea-formaldehyde resin cross-linking agent, preparing method and application thereof |
-
2012
- 2012-02-20 CN CN 201210037076 patent/CN102604021B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519483A (en) * | 2008-04-30 | 2009-09-02 | 北京化工大学 | Novel environment-friendly urea-formaldehyde resin and preparation method thereof |
| CN101585964A (en) * | 2009-04-20 | 2009-11-25 | 永港伟方（北京）科技股份有限公司 | Urea-formaldehyde resin cross-linking agent, preparing method and application thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448178A (en) * | 2013-09-24 | 2015-03-25 | 南京理工大学 | Urea-formaldehyde (UF) resin and method for removing boric acid in boron-containing waste liquor by using same |
| CN104448178B (en) * | 2013-09-24 | 2017-04-19 | 南京理工大学 | Urea-formaldehyde (UF) resin and method for removing boric acid in boron-containing waste liquor by using same |
| CN104059583A (en) * | 2014-06-09 | 2014-09-24 | 杨超 | Preparation method of special urea-formaldehyde resin adhesive for artificial boards |
| CN104194694A (en) * | 2014-08-14 | 2014-12-10 | 广东五联木业集团有限公司 | Preparation method of environment-friendly glue for shaving board |
| CN104388008A (en) * | 2014-10-27 | 2015-03-04 | 深圳市永丽威胶粘科技有限公司 | Environment-friendly no-pollution strapping paper |
| CN105017498A (en) * | 2015-07-03 | 2015-11-04 | 昆明新飞林人造板有限公司 | Preparation method of urea formaldehyde resin for E0 grade particleboards |
| CN105018012A (en) * | 2015-07-28 | 2015-11-04 | 湖北鸿连实业有限公司 | Low-formaldehyde-content glue |
| CN105778839A (en) * | 2016-04-21 | 2016-07-20 | 广西农垦糖业集团良圻制糖有限公司 | Urea-formaldehyde resin glue for bagasse particleboard and preparation method thereof |
| CN105778839B (en) * | 2016-04-21 | 2018-07-17 | 广西农垦糖业集团良圻制糖有限公司 | Urea-formaldehyde resin adhesive for bagasse particleboard and preparation method thereof |
| CN109235120A (en) * | 2018-10-10 | 2019-01-18 | 广州市顺誉装饰材料有限公司 | A kind of environment protecting paper and preparation method thereof |
| CN109485811A (en) * | 2018-10-10 | 2019-03-19 | 中南林业科技大学 | A kind of method that discarded Lauxite degradation recycles |
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| Publication number | Publication date |
|---|---|
| CN102604021B (en) | 2013-12-18 |
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