CN106280245A - Weatherability composite urea formaldehyde resin and production method thereof - Google Patents
Weatherability composite urea formaldehyde resin and production method thereof Download PDFInfo
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- CN106280245A CN106280245A CN201610752515.6A CN201610752515A CN106280245A CN 106280245 A CN106280245 A CN 106280245A CN 201610752515 A CN201610752515 A CN 201610752515A CN 106280245 A CN106280245 A CN 106280245A
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- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 70
- 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 claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- -1 cyanurotriamide modified urea Chemical class 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 229920005610 lignin Polymers 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229940031826 phenolate Drugs 0.000 claims abstract description 21
- 239000002250 absorbent Substances 0.000 claims abstract description 20
- 230000002745 absorbent Effects 0.000 claims abstract description 20
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 18
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 18
- 229920001289 polyvinyl ether Polymers 0.000 claims abstract description 18
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 18
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims abstract description 18
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical group CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 239000002304 perfume Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 61
- 239000002023 wood Substances 0.000 abstract description 23
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 description 35
- 230000001070 adhesive effect Effects 0.000 description 35
- 235000019256 formaldehyde Nutrition 0.000 description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 229920002472 Starch Polymers 0.000 description 12
- 239000008107 starch Substances 0.000 description 12
- 235000019698 starch Nutrition 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 235000013877 carbamide Nutrition 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006009 resin backbone Polymers 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008131 glucosides Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002373 hemiacetals Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 210000001215 vagina Anatomy 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of weatherability composite urea formaldehyde resin and production method thereof, including following raw material: cyanurotriamide modified urea resin；Oxytarch；Polyvinyl alcohol；Hydrogenated rosin；Propanediol polyoxypropylene polyvinylether；Polyisocyanate；Isobutyl triethoxy silane；Phenolate lignin；Clear water；UV absorbent and antioxidant.Production method is: be first put in reactor by clear water, it is heated to 80 100 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane, UV absorbent, antioxidant and propanediol polyoxypropylene polyvinylether, stir 10 minutes to 30 minutes, add polyvinyl alcohol, phenolate lignin, it is allowed to dissolve, add cyanurotriamide modified urea resin and Oxytarch, keep 80 90 DEG C of stirring reactions 25 hours, within 10 20 minutes before use, adding polyisocyanate, mixing and stirring can use.The weatherability composite urea formaldehyde resin resistance to water of the present invention is strong, adhesion strength is high, residual formaldehyde amount is low, good weatherability, as the main binder of wood-based plate, it is possible to increase the weather resistance of wood-based plate.
Description
Technical field
The invention belongs to adhesive production field, particularly a kind of weatherability composite urea formaldehyde resin and production method thereof.
Background technology
Along with development, the raising of living standards of the people of China's economic, the requirement to house decoration the most constantly improves.Wood
Floor, because of its naturally graceful lines, good texture, becomes the preferred material of family's ground surface finishing.And solid wooden compound floor
The shortcoming overcoming solid wooden floor board moisture expansion and drying shrinkage, has preferable dimensional stability, remains the wood naturally of solid wooden floor board simultaneously
Stricture of vagina and comfortable feel, thus become the important kind in floor, produce the Lauxite floor glue that solid wooden compound floor is used
Consumption promotes the most therewith.Lauxite or the maximum adhesive of modified urea-formaldehyde resin glue Nian Jishi China timber industry consumption, account for
More than the 60% of wood-processing industry adhesive total flow, account for about the 90% of wood-based plate glue consumption.Urea-formaldehyde resin adhesive has
Having plurality of advantages, such as higher glue-joint strength, high resistance to cold water performance, to solidify property the fastest, miscible with water good, and easily modulation is suitable
Viscosity and concentration etc., but, current urea-formaldehyde resin adhesive all contains a small amount of active group, easily by the oxygen in environment
Gas or light oxidation Decomposition, cause that adhesive is aging loses effect, causes the wood-based plate quality of outdoor outdoor application to go wrong.
And the many structures from raw material of researcher are started with and furtherd investigate, improve weatherability, substantially increase the cost of adhesive.
Burst size of methanal is restriction particieboard, a key factor of density board development in the market.Due to all kinds of straw
The wood-based plate poor water resistance that the raw material such as stalk, shuck is made, makes bow warping deform because producing expansive force difference after moisture absorption.Cause
This, improve the resistance to water of Lauxite, reduces residual formaldehyde, improves weather resistance, becomes particieboard and density board industry is sent out
The primary problem solved of exhibition.
And cyanurotriamide modified urea resin is to be modified preparing on the basis of Lauxite, Lauxite has former
Expect cheap and easy to get, solidification temperature without advantages such as strict restrictions, but Lauxite boiling water resistance and ageing resistance are poor, because its solidification
After resin in there is hydrophilic free methylol, they are easily combined with water.And the tripolycyanamide of band ring molecule is introduced urea
In urea formaldehyde, form tridimensional network, enclose many hydrophilic groups, change resin backbone structure, promote resin and hand over
Connection, thus reached to improve the adhesion strength of resin, resistance to water and the purpose of weatherability, turn avoid simple tripolycyanamide simultaneously
The shortcoming that formaldehyde resin is relatively costly.
Therefore, how to apply the excellent specific property of cyanurotriamide modified urea resin, give full play to it former as adhesive master
The effect of material, ensure that adhesive has stronger environmental disruption ability of standing after particieboard and density board bond is one simultaneously
It is worth research and valuable problem.
Summary of the invention
For the technological deficiency of above-mentioned existence, it is an object of the invention to provide a kind of weatherability composite urea formaldehyde resin and life thereof
Product method, solves the wood-based plate poor water resistance that the raw materials such as current all kinds of straw, shuck are made, poor because producing expansive force after moisture absorption
Different and the problem that makes bow warping deform, develops that a kind of resistance to water is strong, adhesion strength is high, residual formaldehyde amount is low, good weatherability
Weather-proof composite urea formaldehyde resin.
The technical solution used in the present invention is:
A kind of weatherability composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 50～100 parts；
Oxytarch 20～30 parts；
Polyvinyl alcohol 1～3 parts；
Hydrogenated rosin 3～8 parts；
Propanediol polyoxypropylene polyvinylether 2～3 parts；
Polyisocyanate 4～6 parts；
Isobutyl triethoxy silane 0.5～5 parts；
Phenolate lignin 5～10 parts；
Clear water 100～200 parts；
UV absorbent 1～2 parts；
Antioxidant 1～2 parts.
Described UV absorbent is nano titanium oxide.
Described antioxidant is dibenzylatiooluene.
Cyanurotriamide modified urea resin of the present invention use the cyanurotriamide modified urea resin bought on market or
Use the cyanurotriamide modified urea resin of Guangxi Nanning Green Park Beilin Wood Industry Co., Ltd.'s research, number of patent application: CN
201310353442.X；The applying date: 2013.08.14；Open (bulletin) number: CN 103408711A；Application (patent right) people: wide
Southwest north, Ning Lv garden forest industry company limited, the primary raw material of this cyanurotriamide modified urea resin be formaldehyde, tripolycyanamide and
Carbamide, uses and disposably adds formaldehyde, adds carbamide and the method for tripolycyanamide several times, controls reaction rate, it is to avoid gel
The generation of phenomenon, promotes the reaction completely of formaldehyde.Repeatedly add carbamide, the carbamide every time added and the polymerization rate of formaldehyde
The most different with condition, it is divided into prepolymerization, is polymerized and is polymerized later stage three phases, each stage adds the amount of carbamide and differs
Sample, reaction temperature is the most different, by this technique, it is to avoid the generation of polymerization process gelatin phenomenon, the Lauxite of gained
Narrow molecular weight distribution, residual formaldehyde is low, is used for producing wood-based plate, it is possible to decrease the burst size of methanal of wood-based plate.
Above-described weatherability composite urea formaldehyde resin adhesive, the function of each raw material is as follows:
Cyanurotriamide modified urea resin, for adhesive major ingredient.Urea-formaldehyde resin adhesive is a kind of thermosetting polymer adhesive.
Owing to its technique is simple, cheaper starting materials, the advantages such as adhesive strength is high, water white transparency, be widely used in plywood, particieboard,
The industries such as medium density fibre board (MDF), the production of artificial board and interior decoration, can buy in Market of Adhesives.Band ring molecule
Tripolycyanamide introduce in Lauxite, form tridimensional network, enclose many hydrophilic groups, change resin matrix knot
Structure, promotes resin crosslinks, thus has reached to improve the adhesion strength of resin, resistance to water and the purpose of ageing resistance, the most again
Avoid the shortcoming that simple melamine resin is relatively costly.
Oxytarch be starch in acid, alkali, neutral medium with oxidant effect, make starch oxidation and a kind of change of obtaining
Property starch.Oxytarch product colour is pure white, sticks with paste transparent, good film-forming property, and freeze-thaw resistance is good, is the thickening of low viscosity high concentration
Agent, is widely used in weaving, papermaking, food and Fine Chemical.Oxytarch, can be multiple with more aldehyde radical and carboxyl
During closing Lauxite polymer reaction, generate acetal and hemiacetal structure, thus improve the ageing-resistant performance of Lauxite；
Simultaneous oxidation starch can be combined with the free formaldehyde in cyanurotriamide modified urea resin, can reduce free formaldehyde content；Oxidation
On the other hand starch, can reduce cyanurotriamide modified urea resin addition as viscosity complexing agent again, reduce and produce
Cost.
Polyvinyl alcohol, for toughener so that the wood-based plate intensity produced increases.
Hydrogenated rosin, for antioxidant so that the wood-based plate produced is not easy to go bad, and extends the life-span, anti-aging.
Propanediol polyoxypropylene polyvinylether, for defoamer, prevents adhesive from having bubble cavity to produce during using.
Polyisocyanate is firming agent, is characterized in having the highest wearability, and stable chemical nature, and intensity is high,
The crosslinked action itself having, can improve heat-resisting, water, plasticizer and the performance of solvent of adhesive.
Bridging agent, selects isobutyl triethoxy silane, and its one end can be combined with Lauxite carbonyl, and the other end can be with
The hydroxy combining of starch, strengthens its plank intensity.
Lignin molecular mass after phenolate is reacted reduces, and increases reaction active groups, can eliminate part free formaldehyde.
The preparation method of phenolate lignin is: is placed in separation container by the black liquid using alkaline boiling method slurrying, removes with screen cloth
Undissolved float, settles 4 hours after stirring, discharge lower floor silt, takes the upper strata black liquor vacuum drying containing alkali lignin
Machine carries out vacuum spray drying process, obtains powdery alkali lignin；Take powdery alkali lignin and put in acidifier, add
70wt% sulphuric acid, after stirring, is warming up to 140-160 DEG C, sulfonating reaction 1-2 hour；Evaporate through standard vertical-tubes
Device, circulation rate is 0.4m/s-0.5m/s, and controlling discharging moisture is 30wt%, precipitation, through filtering, being dried to water content
For 15wt%；By lignin: phenol weight ratio is 1:1 addition phenol, control temperature 85-95 DEG C, insulation reaction 1 hour,
Finally i.e. obtain phenolate lignin with 30wt% sodium hydroxide regulation pH to 6.5-7.0.
Nano titanium oxide, as UV absorbent, is fluffy white powder, and diameter, below 100 nanometers, can be inhaled
Receive ultraviolet, can reflect again, scatters ultraviolet, moreover it is possible to through visible ray, have good dispersibility and weatherability, can be used for making up
The fields such as product, functional fibre, plastics, coating, paint and adhesive, as ultraviolet light screener, prevent the infringement of ultraviolet,
Can also be used for superior automobile finish paint.
Dibenzylatiooluene, as antioxidant, can suppress or delay the oxidative degradation of Lauxite to extend the use longevity
Life.Dibenzylatiooluene (BHT) is as anti-oxide, and it can react with the propagating radical in autoxidation, eliminates
Free radical, from but chain reaction interrupt.Dibenzylatiooluene (BHT) both can having given as hydrogen in antioxidation process
Body can also be as free radical trapping agent.Due to 2,6 have 2 strength electron donating groups, therefore, dibenzylatiooluene
(BHT) there is the strongest antioxidant effect.
The preparation of described Oxytarch:
(1), select glass apparatus and assemble synthesizer:
JJ600 electronic balance；Digital display thermostat water bath；Digital display constant speed stirrer；There-necked flask；Electric heating constant-temperature blowing drying box；
NDJ-79 Rotary Viscosimeter.
(2) reagent chemicals:
Raw material: tapioca (moisture 13.8%)；
Reagent: hydrogen peroxide (30%), Copper hydrate, copper sulfate, sodium sulfite (being AR).
(3) preparation principle:
Starch is under oxidant effect, and the hydroxyl oxidable one-tenth carboxyl (-COOH) on glucose unit, it makes binding agent
Stability be improved significantly.Oxidation decreases the quantity of hydroxyl in starch molecule, makes molecular association be obstructed, thus subtracts
The weak binding ability of intermolecular hydrogen chain.Meanwhile, glucosides chain break, make macromolecules degradation, starch molecule amount reduces, thus increases
Dissolubility, mobility and caking property are added.In the presence of liquid caustic soda, the hydroxy combining not oxidized with starch, destroy part hydrogen
Key, makes declines between macromole, thus easy swelling gelatinizing, give its caking property.
Preparation process is as follows:
Weighing 200g tapioca in 1000mL there-necked flask, add water furnishing 18～the starch milk of 21 ° of B é, stirs, slowly
The slow sodium hydroxide solution dripping a certain amount of 5%～7% concentration.After water-bath rises to design temperature, add the copper sulfate of 0.01%.So
A certain amount of hydrogen peroxide of rear addition, after isothermal reaction certain time, adds 0.4g sodium sulfite, and stirring 10min terminates reaction.
Reaction terminate after, with in dilute hydrochloric acid and reacting liquid pH value be 5.5～6.0.Sucking filtration is dehydrated, washes clean, places 40-50 in baking oven
Dry at DEG C, pulverize, sieve and i.e. obtain product.The Oxytarch of above-mentioned use can produce with jumbo reactor.
The production method of a kind of weatherability composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, heating
To 80-100 DEG C, it is subsequently adding the hydrogenated rosin of parts by weight, isobutyl triethoxy silane, nano titanium oxide, dibutyl
Hydroxy-methylbenzene and propanediol polyoxypropylene polyvinylether, stir 10 minutes to 30 minutes, add parts by weight polyvinyl alcohol,
Phenolate lignin, is allowed to dissolve, and adds cyanurotriamide modified urea resin and the Oxytarch of parts by weight, keeps 80-90
DEG C stirring reaction 2-5 hour, 10-20 minute before use add parts by weight polyisocyanate, mixing and stirring
Use.
Compared with prior art, the positive effect of the present invention is:
1, in the present invention, using cyanurotriamide modified urea resin as adhesive major ingredient, have technique simple, raw material is honest and clean
Valency, the advantages such as adhesive strength is high, water white transparency, and the release of low formaldehyde gas, it is a kind of environmental type resin, urea can be improved
The resistance to water of urea formaldehyde, and prevent from glue-line from shrinking reducing internal stress, improve ageing-resistant performance, increases glue solid content, viscosity and just
Viscosity, extends working life.And to use polyvinyl alcohol be toughener so that the wood-based plate intensity produced increases；Use the third two
Alcohol polyoxypropylene polyvinylether, for defoamer, prevents adhesive from having bubble cavity to produce during using；Use polyisocyanate
For firming agent；Selecting isobutyl triethoxy silane as bridging agent, its one end can be combined with Lauxite carbonyl, other end energy
With the hydroxy combining of starch, strengthen its plank intensity；Containing a large amount of active groups in phenolate lignin, as formaldehyde catching agent,
Part free formaldehyde can be eliminated；Use Oxytarch, as viscosity complexing agent, cyanurotriamide modified urea resin can be reduced
Addition, cost-effective；Employing nano titanium oxide is UV absorbent, can absorb ultraviolet, can reflect again, scatter purple
Outside line, has good dispersibility and weatherability, prevents the ultraviolet infringement to adhesive；Use dibenzylatiooluene and hydrogenation
Colophonium is as antioxidant, and dibenzylatiooluene can suppress or delay the oxidative degradation of Lauxite to increase the service life；
Adding hydrogenated rosin makes the wood-based plate produced be not easy to go bad, and extends the life-span, anti-aging.
2, the weatherability composite urea formaldehyde resin that the inventive method production obtains is waterproof, humidity resistance good, as wood-based plate
Main binder, it is possible to increase the sealing property of wood-based plate, makes moisture, moisture be difficult to penetrate into inside wood-based plate, improves wood-based plate
Resistance to water, solve the wood-based plate poor water resistance that the raw materials such as current all kinds of straw, shuck are made, after moisture absorption because of produce expansive force
Difference and make the problem that bow warping deforms.The adhesive major ingredient of the present invention is cyanurotriamide modified urea resin, and by closing
Reason adds antioxidant and ultraviolet absorber elements and ratio so that the adhesive of the present invention has outstanding weather resistance,
Cyanurotriamide modified urea resin, phenolate lignin, bridging agent and other auxiliary agents and effectively cooperation antioxidant and ultraviolet are inhaled
Receipts agent is on the basis of giving full play to adhesive performance, and weather resistance is higher, is suitable for the preparation of weatherability wood-based plate.
Detailed description of the invention
Embodiment 1
A kind of weatherability composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 50 parts；
Oxytarch 20 parts；
Polyvinyl alcohol 1 part；
Hydrogenated rosin 3 parts；
Propanediol polyoxypropylene polyvinylether 2 parts；
Polyisocyanate 4 parts；
Isobutyl triethoxy silane 0.5 part；
Phenolate lignin 5 parts；
100 parts of clear water；
UV absorbent 1 part；
Antioxidant 1 part.
Described UV absorbent is nano titanium oxide.
Described antioxidant is dibenzylatiooluene.
The production method of a kind of weatherability composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 80
DEG C, it is subsequently adding the hydrogenated rosin of parts by weight, isobutyl triethoxy silane, nano titanium oxide, dibenzylatiooluene
With propanediol polyoxypropylene polyvinylether, stir 30 minutes, add the polyvinyl alcohol of parts by weight, phenolate lignin, be allowed to
Dissolve, add cyanurotriamide modified urea resin and the Oxytarch of parts by weight, keep 80 DEG C of stirring reactions 5 hours,
The polyisocyanate using first 10-20 minute to add parts by weight, mixing and stirring can use.
Embodiment 2
A kind of weatherability composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 70 parts；
Oxytarch 24 parts；
Polyvinyl alcohol 2 parts；
Hydrogenated rosin 5 parts；
Propanediol polyoxypropylene polyvinylether 2.4 parts；
Polyisocyanate 5 parts；
Isobutyl triethoxy silane 2 parts；
Phenolate lignin 7 parts；
140 parts of clear water；
UV absorbent 1.4 parts；
Antioxidant 1.4 parts.
Described UV absorbent is nano titanium oxide.
Described antioxidant is dibenzylatiooluene.
The production method of a kind of weatherability composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 85
DEG C, it is subsequently adding the hydrogenated rosin of parts by weight, isobutyl triethoxy silane, nano titanium oxide, dibenzylatiooluene
With propanediol polyoxypropylene polyvinylether, stir 25 minutes, add the polyvinyl alcohol of parts by weight, phenolate lignin, be allowed to
Dissolve, add cyanurotriamide modified urea resin and the Oxytarch of parts by weight, keep 84 DEG C of stirring reactions 4 hours,
The polyisocyanate using first 10-20 minute to add parts by weight, mixing and stirring can use.
Embodiment 3
A kind of weatherability composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 90 parts；
Oxytarch 27 parts；
Polyvinyl alcohol 2.5 parts；
Hydrogenated rosin 7 parts；
Propanediol polyoxypropylene polyvinylether 2.7 parts；
Polyisocyanate 5.5 parts；
Isobutyl triethoxy silane 4 parts；
Phenolate lignin 8 parts；
170 parts of clear water；
UV absorbent 1.7 parts；
Antioxidant 1.7 parts.
Described UV absorbent is nano titanium oxide.
Described antioxidant is dibenzylatiooluene.
The production method of a kind of weatherability composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, heating
To 90 DEG C, it is subsequently adding the hydrogenated rosin of parts by weight, isobutyl triethoxy silane, nano titanium oxide, dibutyl hydroxy
Toluene and propanediol polyoxypropylene polyvinylether, stir 20 minutes, add the polyvinyl alcohol of parts by weight, phenolate lignin,
It is allowed to dissolve, adds cyanurotriamide modified urea resin and the Oxytarch of parts by weight, keep 88 DEG C of stirring reactions 3 little
Time, the polyisocyanate adding parts by weight in 10-20 minute before use, mixing and stirring can use.
Embodiment 4
A kind of weatherability composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 100 parts；
Oxytarch 30 parts；
Polyvinyl alcohol 3 parts；
Hydrogenated rosin 8 parts；
Propanediol polyoxypropylene polyvinylether 3 parts；
Polyisocyanate 6 parts；
Isobutyl triethoxy silane 5 parts；
Phenolate lignin 10 parts；
200 parts of clear water；
UV absorbent 2 parts；
Antioxidant 2 parts.
Described UV absorbent is nano titanium oxide.
Described antioxidant is dibenzylatiooluene.
The production method of a kind of weatherability composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, heating
To 100 DEG C, it is subsequently adding the hydrogenated rosin of parts by weight, isobutyl triethoxy silane, nano titanium oxide, dibutyl hydroxy
Toluene and propanediol polyoxypropylene polyvinylether, stir 10 minutes, add the polyvinyl alcohol of parts by weight, phenolate lignin,
It is allowed to dissolve, adds cyanurotriamide modified urea resin and the Oxytarch of parts by weight, keep 90 DEG C of stirring reactions 2 little
Time, the polyisocyanate adding parts by weight in 10-20 minute before use, mixing and stirring can use.
Comparative example 4
A kind of composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 100 parts；
Oxytarch 30 parts；
Polyvinyl alcohol 3 parts；
Propanediol polyoxypropylene polyvinylether 3 parts；
Polyisocyanate 6 parts；
Isobutyl triethoxy silane 5 parts；
Phenolate lignin 10 parts；
200 parts of clear water.
The production method of a kind of composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 100
DEG C, it is subsequently adding isobutyl triethoxy silane and the propanediol polyoxypropylene polyvinylether of parts by weight, stirs 10 minutes, then
Add the polyvinyl alcohol of parts by weight, phenolate lignin, be allowed to dissolve, add the melamine modified urea-formaldehyde tree of parts by weight
Fat and Oxytarch, keep 90 DEG C of stirrings to react 2 hours, the polyisocyanate adding parts by weight in 10-20 minute before use,
Mixing and stirring can use.
Prepare the weatherability composite urea formaldehyde resin adhesive obtained by embodiment 1-4 and comparative example 4 is compound
Lauxite carries out the mensuration of the residual quantity of formaldehyde respectively, high temperature resistant test, and according to GB/T9846.1-9846.8-2004
In regulation detection bonding strength.Formaldehyde determination uses acetylacetone,2,4-pentanedione spectrophotography, residual formaldehyde %=measured value/sample weight
Amount × %, 25mm), result is as shown in the table: result is as shown in the table:
The embodiment 4 difference from comparative example 4 is, embodiment 4 adds UV absorbent and antioxidant；And it is right
UV absorbent and antioxidant is not added than embodiment 4.But the data by embodiment 4 and comparative example 4 are permissible
Finding out, both residual formaldehyde and the physical index change of bonding strength are inconspicuous, but tensile shear strength, hot strength
But differ bigger with impact strength, the tensile shear strength of embodiment 4 is 38.7 Mpa, hot strength 42.5 Mpa, impact
Intensity is 63 Mpa, and the tensile shear strength of comparative example 4 is 42.4Mpa, hot strength 44.7 Mpa, and impact strength is 71
Mpa.In the present invention, employing nano titanium oxide is UV absorbent, can absorb ultraviolet, can reflect again, scatter purple
Outside line, has good dispersibility and weatherability, prevents the ultraviolet infringement to adhesive；Use dibenzylatiooluene and hydrogenation
Colophonium is as antioxidant, and dibenzylatiooluene can suppress or delay the oxidative degradation of Lauxite to increase the service life；
Adding hydrogenated rosin makes the wood-based plate produced be not easy to go bad, and extends the life-span, anti-aging.
Compare with the urea-formaldehyde resin adhesive data market from the data of embodiment 1-4, find that the present invention's is weather-proof
Property composite urea formaldehyde resin adhesive residual formaldehyde less than the urea-formaldehyde resin adhesive on market, its bonding strength, to stretch shearing strong
Degree, hot strength and impact strength are slightly better than the urea-formaldehyde resin adhesive on market, and it it is critical only that the adhesive master of the present invention
Material is cyanurotriamide modified urea resin, and buys the urea-formaldehyde resin adhesive returned on market, and its Lauxite major part is all
It is that its weather resistance, bonding strength and residual formaldehyde amount aspect are not as through cyanurotriamide modified mistake not through modification
Lauxite is good.Because the tripolycyanamide of band ring molecule is incorporated in Lauxite, tridimensional network can be formed, close
Many hydrophilic groups, change resin backbone structure, promote resin crosslinks, thus the bonding having reached to improve resin is strong
Degree, resistance to water and the purpose of ageing resistance.Further, the present invention adds nano titanium oxide in composite urea formaldehyde resin is ultraviolet
Light absorbers, can absorb ultraviolet, can reflect again, scatters ultraviolet, has good dispersibility and weatherability, prevents ultraviolet
Infringement to adhesive；Use dibenzylatiooluene and hydrogenated rosin as antioxidant, play weather-proof effect altogether.Dibutyl hydroxyl
Base toluene can suppress or delay the oxidative degradation of Lauxite to increase the service life；Add what hydrogenated rosin made to produce
Wood-based plate is not easy to go bad, and extends the life-span, anti-aging.
By upper table it can also be seen that the urea that is below on market of the weatherability composite urea formaldehyde resin residual formaldehyde of the present invention
Urea formaldehyde, uses safety coefficient high, and bonding strength is the most excellent relative to Lauxite；Meanwhile, the weatherability of the present invention is combined
Urea-formaldehyde resin adhesive weather resistance is high compared with the Lauxite on market.Visible, the weatherability composite urea formaldehyde resin glue of the present invention
Glutinous agent not only has the advantages such as high, the use safety of bonding strength, also has shear strength moderate, and viscosity is handling by force, weatherability
Strong feature, has great promotional value.
Claims (4)
1. a weatherability composite urea formaldehyde resin, it is characterised in that: it is made up of the raw material of following parts by weight:
Cyanurotriamide modified urea resin 50～100 parts；
Oxytarch 20～30 parts；
Polyvinyl alcohol 1～3 parts；
Hydrogenated rosin 3～8 parts；
Propanediol polyoxypropylene polyvinylether 2～3 parts；
Polyisocyanate 4～6 parts；
Isobutyl triethoxy silane 0.5～5 parts；
Phenolate lignin 5～10 parts；
Clear water 100～200 parts；
UV absorbent 1～2 parts；
Antioxidant 1～2 parts.
Weatherability composite urea formaldehyde resin the most according to claim 1, it is characterised in that: described UV absorbent is for receiving
Rice titanium dioxide.
Weatherability composite urea formaldehyde resin the most according to claim 1, it is characterised in that: described antioxidant dibutyl hydroxyl
Base toluene.
Weatherability composite urea formaldehyde resin the most according to claim 1, it is characterised in that: the life of weatherability composite urea formaldehyde resin
Product method: be first put in reactor by the clear water of parts by weight, be heated to 80-100 DEG C, is subsequently adding the hydrogenation pine of parts by weight
Perfume, isobutyl triethoxy silane, UV absorbent, antioxidant and propanediol polyoxypropylene polyvinylether, stir 10 points
Clock, to 30 minutes, adds the polyvinyl alcohol of parts by weight, phenolate lignin, is allowed to dissolve, add the trimerization of parts by weight
Cyanamide modified urea-formaldehyde resin and Oxytarch, keep 80-90 DEG C of stirring reaction 2-5 hour, within 10-20 minute before use, add weight
The polyisocyanate of amount number, mixing and stirring can use.
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