CN103965425A - Preparation method for water-glass modified amino resin - Google Patents
Preparation method for water-glass modified amino resin Download PDFInfo
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- CN103965425A CN103965425A CN201310053870.0A CN201310053870A CN103965425A CN 103965425 A CN103965425 A CN 103965425A CN 201310053870 A CN201310053870 A CN 201310053870A CN 103965425 A CN103965425 A CN 103965425A
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- China
- Prior art keywords
- urea
- preparation
- water glass
- formaldehyde
- value
- Prior art date
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- Pending
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- 235000019353 potassium silicate Nutrition 0.000 title claims abstract description 26
- 229920003180 amino resin Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 55
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 25
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 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 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 3
- 230000005494 condensation Effects 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000001339 acylated starch Substances 0.000 claims 1
- 235000013829 acylated starch Nutrition 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 239000011120 plywood Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000011094 fiberboard Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- -1 waterproof templates Substances 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 14
- 238000000034 method Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000219000 Populus Species 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method for water-glass modified amino resin. According to the preparation method, water glass is employed to replace sodium hydroxide for reacting with urea and formaldehyde and further for forming an inorganically organically combined silicon-oxygen bond. The molar ratio of formaldehyde to urea is 1.1-1.86:1 during reaction, water glass accounting for 1-6% by weight of urea is employed for modification, and urea is added into formaldehyde in 2-4 proportions. The preparation method helps to improve the resin structure and improve the bonding strength, and also helps to reduce the manufacturing cost. The synthesized resin is applicable to produce multi-plywoods, block boards, floor base materials, waterproof templates, particle boards and medium-density fiberboards, and also is applicable to E1-level artificial plates.
Description
Technical field
The present invention relates to a kind of preparation method of modified aminoresin, more particularly, it relates to a kind of preparation method of modifying water glass aminoresin.
Background technology
Be accompanied by the fast development of China's reform and opening-up, wood-based panel industry has obtained the development of advancing by leaps and bounds.In Wood-based Panel Production, aminoresin is most widely used general, tackiness agent that market demand is maximum in wood working, but exists easy release formaldehyde when producing and using to cause the unfavorable factors such as environmental pollution.In document, adopt the preparation method of the mol ratio that reduces formaldehyde and urea more, also effective at home and abroad, but bring the drawbacks such as the water-fast splicing strength decreased of sheet material.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, a kind of preparation method of modifying water glass aminoresin is provided, produce one and there is inorganic-organic dual nature, cost is low, content of free aldehyde is low, the processing performances such as ageing resistance, water tolerance, flame resistivity, thermostability are good, and can significantly improve the resin of glued board gummed performance.Because hardness after adhesive solidification improves, more can effectively prevent the glued board distortion warpage of making moist.
Object of the present invention is achieved by following technical proposals: modifying water glass aminoresin of the present invention is made up of following steps, the described modifying water glass that is modified as, formaldehyde solution is added after reactor, drop into properties-correcting agent water glass, making solution pH value is 7～9, be heated to 45～50 DEG C, react 10～25 minutes.Then add first urea, the mol ratio that makes urea and formaldehyde is 1: 2.3～3.0, adds 0.1～2% (weight) that linking agent 1 its amount is urea total amount.Temperature is controlled at 90 ± 2 DEG C, and pH value is 7.6～8.5, keeps 30～410 minutes.Add linking agent 2, its amount is 2～10% of urea total amount.Maintaining pH value with modifying water glass is 7.6～8.5, and adding second batch urea to make the mol ratio of urea and formaldehyde is 1: 1.8～2.1, maintains 30～40 minutes at 90 ± 2 DEG C.Adjusting pH value is 4～6, react to 25 DEG C of viscosity be coated with-4 glasss 22～25 seconds.Adjusting pH value is 7～8, adds the 3rd batch of urea, and the mol ratio that makes urea and formaldehyde is 1: 1.4～1.6.90 ± 2 DEG C of reactions 20～30 minutes.Be cooled to 70 ± 5 DEG C and add the 4th batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.05～1.4, is incubated 20～30 minutes, cools to subsequently below 40 DEG C discharging.Wherein the concentration of formaldehyde is 36.5～37%.
Compared with prior art, advantage of the present invention is:
1, the inventive method, by modifying water glass, is introduced the inorganic siloxane bond with organically combining, and forms through addition, polycondensation the netted build structural resin that contains siloxane bond, not only improves resin structure and improves bonding strength, has reduced manufacturing cost simultaneously.
2, in production process, do not dewater, do not need formaldehyde sewage disposal operation, therefore manufacturing process is simple, and cost is low.
3, for the production of this synthetic resins free formaldehyde content of multiplying plywood, core-board, floor base material lower than 0.15%, solids content 52～60%, this glue also can be used for producing E1 level wood-based plate.
4, owing to adopting modifying water glass, after adhesive solidification, hardness improves, and more can effectively prevent glued board make moist distortion, warpage.
Embodiment:
Describe the present invention in detail below by embodiment, but be not limited to this.
Embodiment
1, composition of raw materials
2, synthesis technique
By above-mentioned raw materials formula, formaldehyde is added in reactor, slowly add water glass and formaldehyde reaction under stirring, making solution pH value is 7～9, be heated to 45 DEG C, react 15 minutes, add first urea, steadily be warming up to 90 ± 2 DEG C, be incubated half an hour and complete methylolation.Add trimeric cyanamide, water glass, second batch urea, maintaining pH value is 7.6～8.5, keep 40 minutes at 90 ± 2 DEG C, adjusting pH value with formic acid is 4～6, react to 25 DEG C of viscosity be coated with-4 glasss 22～25 seconds, adding water glass to keep pH value is 7～8 to add the 3rd batch of urea, keep 30 minutes at 90 ± 2 DEG C, be cooled to 70 ± 5 DEG C and add residue urea, be incubated 30 minutes, lower the temperature subsequently 40 DEG C to lower pH value as 7～8 dischargings.
Comparative example
1, in resin formula, cancel water glass, substitute all the other same embodiment with aqueous sodium hydroxide solution.
2, synthesis technique
Adopt 30% aqueous sodium hydroxide solution to regulate pH value, all the other press embodiment operation.
Experimental example
(mol ratio is 1: 1.1 to adopt the embodiment of the present invention, solid content 54%) obtain modifying water glass amino resin adhesive and comparative example (mol ratio is 1: 1.1, solid content 54%) obtain common amino resin adhesive produce respectively seven layers of glued board test specimen 1 and test specimen 2.When gluing, add weight resin 20～25% flour and 0.5% ammonium chloride and auxiliary agent B (providing for oneself).
Veneer is 1.7mm poplar heat pressing process: pressure 1.0～1.5Mpa
Temperature: 115 ± 5 DEG C of time: 60～90s/mm
Measure the burst size of methanal of test specimen 1,2 by moisture eliminator method, measure the bonding strength of test specimen 1,2 by the regulation of GB/T17657-1999 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels ", its burst size of methanal and bonding strength are in table 1
Table 1
From table 1, the modifying water glass amino resin adhesive that utilizes the inventive method to produce is manufactured multi-ply wood, the bonding strength of product can meet II class National Standards for Plywood (being not less than 0.7Mpa), and burst size of methanal can meet national E1 level (being not more than 1.mg/l) standard.
Claims (5)
1. a preparation method for modifying water glass aminoresin, is characterized in that, with formaldehyde and urea mol ratio 1.1～1.86: 1, adds linking agent; Urea divides 2～4 batches to add in formaldehyde, with 1～6% modifying water glass of weight of urea, form through addition, condensation the netted build structural resin that contains siloxane bond, the pH value of the production process hierarchy of control is: the methylolated pH value of formaldehyde and urea is 7～9, the pH value of condensation is 4～6, and it is 7～8 that reaction finishes that rear pH value is adjusted into.
2. the preparation method of modifying water glass aminoresin according to claim 1, is characterized in that, described water glass is modulus 2.8～3.0, solid content 48～50%, and consumption is 1～6% of urea total amount.
3. the preparation method of modifying water glass aminoresin according to claim 1, is characterized in that, described dosage of crosslinking agent is 0.1～72% of urea total amount.
4. the preparation method of modifying water glass aminoresin according to claim 1, is characterized in that, described linking agent is at least one in phenol, polyvinyl alcohol, acylated starch, Dyhard RU 100, trimeric cyanamide or isocyanic ester.
5. the preparation method of modifying water glass aminoresin according to claim 1, is characterized in that, the acid that described condensation stage pH value conditioning agent uses is selected from least one in sulfuric acid, hydrochloric acid, phosphoric acid, formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310053870.0A CN103965425A (en) | 2013-02-02 | 2013-02-02 | Preparation method for water-glass modified amino resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310053870.0A CN103965425A (en) | 2013-02-02 | 2013-02-02 | Preparation method for water-glass modified amino resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103965425A true CN103965425A (en) | 2014-08-06 |
Family
ID=51235464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310053870.0A Pending CN103965425A (en) | 2013-02-02 | 2013-02-02 | Preparation method for water-glass modified amino resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965425A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185600A (en) * | 2017-05-09 | 2017-09-22 | 安徽皖东化工有限公司 | A kind of preparation technology of groundwater treatment macroporous anion exchange resin |
| CN107321394A (en) * | 2017-05-09 | 2017-11-07 | 安徽皖东化工有限公司 | A kind of sewage disposal anion exchange resin preparation method |
| CN108409279A (en) * | 2018-02-10 | 2018-08-17 | 贵港市万升木业有限公司 | A method of sawdust is discarded using pine and prepares light decorative plate as raw material |
| CN110862774A (en) * | 2019-12-06 | 2020-03-06 | 成都原创人造板科学技术有限公司 | Modified inorganic adhesive, preparation method and application in production of wood-based panels |
| CN113999357A (en) * | 2021-11-12 | 2022-02-01 | 嘉兴柯程科技有限责任公司 | Transparent fireproof rubber plate, laminated fireproof glass and preparation method thereof |
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|---|---|---|---|---|
| CN1086224A (en) * | 1993-08-20 | 1994-05-04 | 山东省鱼台县合成胶厂 | A kind of modified urea-formaldehyde resin and production technique thereof |
| CN1834186A (en) * | 2006-03-15 | 2006-09-20 | 北京林业大学 | Cyanurotriamide modified urea resin and prepn. process |
| CN101113274A (en) * | 2006-07-28 | 2008-01-30 | 中宏（天津）实业有限公司 | Flame-proof waterproofing paint |
| CN102443369A (en) * | 2011-10-31 | 2012-05-09 | 东莞市山力高分子材料科研有限公司 | Wood adhesive and preparation method thereof |
-
2013
- 2013-02-02 CN CN201310053870.0A patent/CN103965425A/en active Pending
Patent Citations (4)
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| CN1086224A (en) * | 1993-08-20 | 1994-05-04 | 山东省鱼台县合成胶厂 | A kind of modified urea-formaldehyde resin and production technique thereof |
| CN1834186A (en) * | 2006-03-15 | 2006-09-20 | 北京林业大学 | Cyanurotriamide modified urea resin and prepn. process |
| CN101113274A (en) * | 2006-07-28 | 2008-01-30 | 中宏（天津）实业有限公司 | Flame-proof waterproofing paint |
| CN102443369A (en) * | 2011-10-31 | 2012-05-09 | 东莞市山力高分子材料科研有限公司 | Wood adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 顾继友等: "《胶黏剂与涂料》", 30 September 2012, 中国林业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185600A (en) * | 2017-05-09 | 2017-09-22 | 安徽皖东化工有限公司 | A kind of preparation technology of groundwater treatment macroporous anion exchange resin |
| CN107321394A (en) * | 2017-05-09 | 2017-11-07 | 安徽皖东化工有限公司 | A kind of sewage disposal anion exchange resin preparation method |
| CN108409279A (en) * | 2018-02-10 | 2018-08-17 | 贵港市万升木业有限公司 | A method of sawdust is discarded using pine and prepares light decorative plate as raw material |
| CN110862774A (en) * | 2019-12-06 | 2020-03-06 | 成都原创人造板科学技术有限公司 | Modified inorganic adhesive, preparation method and application in production of wood-based panels |
| CN110862774B (en) * | 2019-12-06 | 2021-11-30 | 成都原创人造板科学技术有限公司 | Modified inorganic adhesive, preparation method and application in production of wood-based panel |
| CN113999357A (en) * | 2021-11-12 | 2022-02-01 | 嘉兴柯程科技有限责任公司 | Transparent fireproof rubber plate, laminated fireproof glass and preparation method thereof |
| CN113999357B (en) * | 2021-11-12 | 2024-01-30 | 嘉兴柯程科技有限责任公司 | Transparent fireproof adhesive plate, adhesive-laminated fireproof glass and preparation method thereof |
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Application publication date: 20140806 |