CN103834337B - Method for converting ordinary phenolic resin into quick-curing wood structure adhesive - Google Patents
Method for converting ordinary phenolic resin into quick-curing wood structure adhesive Download PDFInfo
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- CN103834337B CN103834337B CN201410106371.8A CN201410106371A CN103834337B CN 103834337 B CN103834337 B CN 103834337B CN 201410106371 A CN201410106371 A CN 201410106371A CN 103834337 B CN103834337 B CN 103834337B
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- phenolic resin
- solids content
- phenol
- tackiness agent
- formaldehyde
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 41
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002023 wood Substances 0.000 title claims abstract description 29
- 239000000853 adhesive Substances 0.000 title abstract description 15
- 230000001070 adhesive effect Effects 0.000 title abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 80
- 239000000843 powder Substances 0.000 claims description 30
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012745 toughening agent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 239000005996 Blood meal Substances 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 5
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 244000061456 Solanum tuberosum Species 0.000 claims description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000013312 flour Nutrition 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 5
- 229940100630 metacresol Drugs 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 150000000469 3,5-xylenols Chemical class 0.000 claims 2
- 238000004026 adhesive bonding Methods 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- 239000003623 enhancer Substances 0.000 abstract 1
- 230000001788 irregular Effects 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 230000036314 physical performance Effects 0.000 abstract 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract 1
- 229920003987 resole Polymers 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000002852 3,5-xylenyl group Chemical class [H]C1=C(O*)C([H])=C(C([H])=C1C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QDNBHWFDWXWFTG-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1.OC1=CC=CC(O)=C1 QDNBHWFDWXWFTG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZXSBYAWLZRAJJY-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde phenol Chemical compound C1(O)=C(C(O)=CC=C1)C=O.OC1=CC=CC=C1 ZXSBYAWLZRAJJY-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention discloses a method for converting ordinary phenolic resin into a quick-curing wood structure adhesive. The method comprises the following steps: (1) preparing an adhesive main agent; (2) preparing a curing agent; and (3) mixing the adhesive main agent and the curing agent in a certain ratio to obtain a wood-structure adhesive capable of rapidly curing under a hot pressing or cold pressing condition. The method has the advantages that the phenolic resin is ordinary commercially-available or finished thermoplastic or thermosetting phenolic resin, and is copolymerized and condensed together with an enhancer under the conditions of certain pH value and temperature to obtain the adhesive main agent; a main curing agent and an extender are mixed in a certain ratio to obtain the curing agent; the prepared wood structure adhesive has the advantages of dual components, long shelf life, high gluing strength, water resistance, weather resistance, capability of curing under the condition of hot pressing or cold pressing, low curing temperature and short curing time. The method is standard in process, easy and convenient to operate, and easy to implement. The wood structure adhesive is applied to machining of various irregular and large-sized wood structure members such as GLULAM, solid wood glued beams, solid wood glued columns and I-shaped beams, as well as products such as large-sized solid wood glued furniture, and is superior in physical performance and weather resistance.
Description
Technical field
What the present invention relates to is a kind of method common thermoplastic or heat-reactive phenolic resin being changed into fast setting timber structure tackiness agent, belongs to wood adhesive and manufactures field.
Background technology
Phenol formaldehyde resin tackiness agent (PF) has excellent physical and mechanical property and ageing-resistant performance due to it, it is the preferred adhesives of producing the excellent Structural Laminated Wood of high-intensity weather-proof high, its shortcoming is that solidification value is high, set time is long, therefore needs specific installation could be used in large span, large format, the processing of superthick Structural Laminated Wood.The glue performance of resorcinol formaldehyde resin tackiness agent and excellent weather resistance and hard are in phenol formaldehyde resin tackiness agent, especially require that bonding strength is high, outdoor laminated structure many employings resorcinol formaldehyde resin tackiness agent of moisture resistant and good weatherability, this tackiness agent can at middle temperature and cured at room temperature, but the activity phase is extremely short after it adds solidifying agent, generally be no more than 30min, make it still cannot adapt to large span, large format, superthick Structural Laminated Wood adhesive technology, it is expensive in addition, also limit it Structural Laminated Wood glued joint on use.
" Luo Wenshi (1990). the development of resorcinol phenol formaldehyde resin with gluing together the application on wooden frame [J]. timber industry (03): 14-19. "; " Wang Chunpeng (1999). resorcinol phenol formaldehyde resin preparation and property research [J]. chemistry of forest product and industry (04): 23-28. "; " Huang Yan (2002). the research [J] of phenol-resorcinol-formaldehyde tackiness agent one step copolycondensation synthesis. chemical engineer (04): 16-18. "; " Zhang Yifu (2002). the study on the synthesis [J] of copolycondensation Resorcinol modified phenolic adhesive. bonding (01): 19-21. "; " Korea Spro builds (2005). the research [J] of Resorcinol copolymerization PF resin solidification characteristic and effect. Chinese tackiness agent (08): 5-8. " etc. report by phenol, Resorcinol, formaldehyde method for ternary polymerization, obtain performance close to but cost lower than the timber structure tackiness agent of pure resorcinol formaldehyde resin, described synthesis technique is single stage method or two-step approach is all with phenol, Resorcinol and the formaldehyde monomers unit starting point for synthesis, follow phenolic resin synthesis technique, technique relative maturity.Application number 201010200167.4, publication number are that the name of CN101864053A is called in " modified phenolic resin for bamboo structure material and preparation method thereof " that relating to by phenolic aldehyde storing liquid is initiator, the method of synthesis modification resol, described storage liquid is after simply being mixed by the weight percent of 2-85%:98-15% with formaldehyde by phenol, add Resorcinol after adding formaldehyde and alkali temperature reaction more in proportion, it is different that this technique and the method that Luo Wenshi etc. reports there is no in essence.Application number 201210541988.3, publication number are that the name of CN103012703A is called in the phenolic resin modified method related in " a kind of intermediate-temperature curing type phenolic resin and preparation method thereof ", except interpolation Resorcinol, still need and add urea, trimeric cyanamide, soybean protein isolate etc., though modified phenolic resins energy intermediate temperature setting, synthesis technique there is no obvious simplification.
Summary of the invention
What the present invention proposed is a kind of method phenolic resin being changed into fast setting timber structure tackiness agent, its object is to the above-mentioned defect overcome existing for prior art, with commercially available or finished product resol for synthesis initiator, synthesis technique is relatively simple, energy consumption is lower, can quick-setting modified phenolic resins novel method.This modified phenolic resins hot pressing or solidification of colding pressing, solidification value is low, set time is short, can be used for different shape size, in the Product processing such as the wood structures such as especially irregularly shaped and large size GLULAM, glued wood beam, glued wood post, I-beam and Large Real wood veneered furniture.
Technical solution of the present invention: the method common (commercially available or finished product) resol being changed into fast setting timber structure tackiness agent, comprises following processing step:
1) tackiness agent host preparation;
2) solidifying agent preparation;
3) tackiness agent host, main solidifying agent and extender by weight scope be 100:5-30:5-30 ratio mixing, be formed in hot pressing (mainly for the following sheet material of assembly thickness 100mm, hot pressing time: 0.5-1min/mm, temperature: 80-140 DEG C, unit pressure: 0.5-1.2MPa) or cold pressing (mainly for the above sheet material of assembly thickness 100mm, time: 2-8h, temperature: room temperature; Unit pressure: 0.5-1.2MPa) fast setting timber structure tackiness agent under condition.
Advantage of the present invention: with common commercially available or finished product thermoplastic or heat-reactive phenolic resin for synthesis initiator, make tackiness agent host with toughener copolymeric condensation under certain pH value and temperature condition; Main solidifying agent (formaldehyde solution (more than 35% concentration), oxalic dialdehyde (more than 40% concentration), paraformaldehyde or hexamethylenetetramine) is mixed mutually with extender (flour, bean powder, potato powder, blood meal, wood powder, tree bark powder, seed hulls powder, straw powder), take mixture as solidifying agent, all curable under making two-pack, shelf lives length, bonding strength degree, water-fast, weather-proof, hot pressing or condition of colding pressing thus, and solidification value is low, the timber structure tackiness agent that set time is short.Technological specification, easy and simple to handle, easily implement, for different shape size, in the Product processing such as the wood structures such as especially irregularly shaped and large size GLULAM, glued wood beam, glued wood post, I-beam and Large Real wood veneered furniture, there is excellent physical and mechanical property and weather resistance.
Embodiment
Phenolic resin is changed into the method for fast setting timber structure tackiness agent, comprises following processing step:
1) tackiness agent host preparation;
2) solidifying agent preparation;
3) tackiness agent host, main solidifying agent and extender by weight scope be 100:5-30:5-30 ratio mixing, be formed in hot pressing (for the following sheet material of assembly thickness 100mm, hot pressing time: 0.5-1min/mm, temperature: 80-140 DEG C, unit pressure: 0.5-1.2MPa) or cold pressing (for the above sheet material of assembly thickness 100mm, time: 2-8h, temperature: room temperature; Unit pressure: 0.5-1.2MPa) fast setting timber structure tackiness agent under condition.
Described processing step 1) preparation of tackiness agent host be with common (commercially available or finished product) thermoplastic or heat-reactive phenolic resin for raw material, under predetermined pH value and temperature condition, make tackiness agent host with toughener copolymeric condensation.
Described processing step 2) preparation of solidifying agent, comprising:
1) formaldehyde solution (gauge with dry-matter), the concentration that are more than 35% with mass concentration are the glyoxal solution (gauge with dry-matter) of more than 40%, the one in paraformaldehyde or hexamethylenetetramine is main solidifying agent;
2) will solidify host to mix with extender, the weight part ratio scope of wherein solidifying host and extender is 5-30:5-30.
Described extender, comprises flour, bean powder, potato powder, blood meal, wood powder, tree bark powder, seed hulls powder or straw powder.
Described novolac resin refers to that formaldehyde (F) is less than 1(F/P≤1 with the mol ratio of phenol (P)), the water-soluble obtained through acid, alkaline or divalent-metal ion catalyst or the common commercially available or finished product resol of ethanol-soluble type (mainly referring to ethanol); Described heat-reactive phenolic resin refers to that formaldehyde (F) is greater than 1(F/P > 1 with the mol ratio of phenol (P)), the water-soluble obtained through acid, alkaline or divalent-metal ion catalyst or the common commercially available or finished product resol of ethanol-soluble type (mainly referring to ethanol); Described toughener is the Resorcinol of technical grade, Metha Amino Phenon, Phloroglucinol monomethyl ether, 3,5 xylenols, the one in meta-cresol.
Described common (commercially available or finished product) thermoplasticity or heat-reactive phenolic resin, adopt the mode of dilution or devolatilization (fugitive constituent) to adjust its solids content at 40-60%; When solids content is greater than 60%, add alcohol or thin up, the addition of ethanol or water is to make the solids content of phenol resin solution between 40-60%, and final solids content is determined according to actual needs; When solids content lower than 40% time then dewater or dealcoholysis, deviate from amount to make the solids content of phenol resin solution between 40-60%, final solids content is determined according to actual needs.
Described solids content must add the formalin of mass concentration more than 35% at the novolac resin of 40-60%, and make its mol ratio (F/P) >=1.4, formalin addition is depending on final mol ratio or according to actual needs; The heat-reactive phenolic resin of described solids content between 40-60%, as initial molar ratio 1 < (F/P) < 1.4, must add the formalin of mass concentration more than 35% and make its mol ratio (F/P) >=1.4, formalin addition is depending on final mol ratio or according to actual needs; The heat-reactive phenolic resin of described solids content between 40-60%, its initial molar ratio (F/P) >=1.4, then add or do not add the formalin of more than 35% concentration, depending on final mol ratio or according to actual needs.
Described solids content is between 40-60%, and the phenol resin solution of final mol ratio >=1.4 need be that the sodium hydroxide of 30-40% or potassium hydroxide solution adjust ph are at 9-13 by mass concentration.
Described solids content is at 40-60%, and final mol ratio (F/P) >=1.4, pH value is at the phenol resin solution of 9-13, and viscosity when its 25 DEG C should between 200-300mPas.Viscosity < 200mPas when 25 DEG C, then temperature reaction, range of reaction temperature, at 50-100 DEG C, makes its viscosity reach 200-300mPas, is then cooled to less than 50 DEG C.Need to add toughener in the phenol resin solution of viscosity between 200-300mPas, toughener refers to the Resorcinol of technical grade, Metha Amino Phenon, Phloroglucinol monomethyl ether, 3,5 xylenols, one in the aldehydes matters such as meta-cresol, addition drops to 0.5-0.9 with the mol ratio of formaldehyde after making interpolation toughener and total aldehydes matter; And insulation reaction, temperature of reaction remains on less than 60 DEG C, when reaction end viscosity controller is between 300-500mPas, is cooled to room temperature storage; Make the host of tackiness agent thus.
Described solidifying agent host to be mass concentration be more than 35% formaldehyde solution, concentration be more than 40% glyoxal solution be with dry-matter gauge, paraformaldehyde is ground to more than 200 orders, and hexamethylenetetramine is ground to more than 200 orders; Extender comprises flour, bean powder, potato powder, blood meal, wood powder, tree bark powder, seed hulls powder or straw powder, is all crushed to more than 100 orders.
Embodiment
The formaldehyde amount of required interpolation when being adjusted to mol ratio (>=1.4) by initial molar ratio (< 1.4) obtains according to following formulae discovery:
When initial solids content >=60%, to when adjusting between final solids content 40-60%, water need be added or alcohol consumption obtains according to following formulae discovery:
When initial solids content≤40%, to when adjusting between final solids content 40-60%, water need be deviate from or alcohol consumption obtains according to following formulae discovery:
When adding toughener and making the mol ratio of total aldehydes matter drop between 0.5-1.0, the addition of toughener obtains according to following formulae discovery:
The above
p 1,
n 1,
w 1,
w 2,
w 3and
q 1to the consulting of related production producer or can measure according to concerned countries standard oneself, be easy to obtain.
Be described further the present invention below in conjunction with embodiment, but protection scope of the present invention is not limited to embodiment, the equivalence that related personnel does with technical solution of the present invention changes, and all belongs in scope.
The each embodiment of described timber structure tackiness agent host is raw materials used and with scale, as table 1.Wherein
p 2take Resorcinol as basis, the same Resorcinol of calculating of other tougheners (Metha Amino Phenon, Phloroglucinol monomethyl ether, 3,5 xylenols, meta-cresol etc.).
Table 1
| Host embodiment | P 1 | n 1 | n 2 | n 3 | w 1 | w 2 | w 3 | Q 1 | Q 2 | F 1 | P 2 | W 1 | W 2 |
| 1 | 50 | 0.5 | 1.4 | 0.5 | 0.35 | 0.95 | 0.95 | 0.90 | 0.40 | 38.98 | 105.32 | 100 | 125 |
| 2 | 50 | 0.6 | 1.5 | 0.6 | 0.36 | 0.96 | 0.96 | 0.80 | 0.41 | 38.30 | 87.77 | 100 | 95.12 |
| 3 | 50 | 0.7 | 1.6 | 0.7 | 0.37 | 0.97 | 0.97 | 0.70 | 0.42 | 37.65 | 75.23 | 100 | 66.67 |
| 4 | 50 | 0.8 | 1.7 | 0.8 | 0.38 | 0.98 | 0.98 | 0.60 | 0.43 | 37.04 | 65.82 | 100 | 39.53 |
| 5 | 50 | 0.9 | 1.8 | 0.9 | 0.39 | 0.99 | 0.99 | 0.50 | 0.44 | 36.46 | 58.51 | 100 | 13.64 |
| 6 | 50 | 1 | 1.9 | 1 | 0.40 | 1.00 | 1.00 | 0.50 | 0.45 | 35.90 | 52.66 | 100 | 11.11 |
| 7 | 50 | 1.1 | 2 | 0.5 | 0.41 | 0.95 | 0.95 | 0.49 | 0.46 | 33.28 | 175.53 | 100 | 6.52 |
| 8 | 50 | 1.2 | 2.1 | 0.6 | 0.42 | 0.96 | 0.96 | 0.48 | 0.47 | 32.83 | 146.28 | 100 | 2.13 |
| 9 | 50 | 1.3 | 2.2 | 0.7 | 0.43 | 0.97 | 0.97 | 0.48 | 0.48 | 32.40 | 125.38 | 100 | 0 |
| 10 | 50 | 1.4 | 1.4 | 0.8 | 0.44 | 0.98 | 0.98 | 0.46 | 0.49 | 0.00 | 43.89 | 100 | 6.12 |
| 11 | 50 | 1.5 | 1.5 | 0.9 | 0.45 | 0.99 | 0.99 | 0.45 | 0.50 | 0.00 | 39.01 | 100 | 10.00 |
| 12 | 50 | 1.6 | 1.6 | 1 | 0.46 | 1.00 | 1.00 | 0.44 | 0.51 | 0.00 | 35.11 | 100 | 13.73 |
| 13 | 50 | 1.7 | 1.7 | 0.5 | 0.47 | 0.95 | 0.95 | 0.43 | 0.52 | 0.00 | 140.43 | 100 | 17.31 |
| 14 | 50 | 1.8 | 1.8 | 0.6 | 0.48 | 0.96 | 0.96 | 0.42 | 0.53 | 0.00 | 117.02 | 100 | 20.75 |
| 15 | 50 | 1.9 | 1.9 | 0.7 | 0.49 | 0.97 | 0.97 | 0.41 | 0.54 | 0.00 | 100.30 | 100 | 24.07 |
| 16 | 50 | 2 | 2 | 0.8 | 0.50 | 0.98 | 0.98 | 0.40 | 0.55 | 0.00 | 87.77 | 100 | 27.27 |
| 17 | 50 | 2.1 | 2.1 | 0.9 | 0.51 | 0.99 | 0.99 | 0.39 | 0.56 | 0.00 | 78.01 | 100 | 30.36 |
| 18 | 50 | 2.2 | 2.2 | 1 | 0.52 | 1.00 | 1.00 | 0.38 | 0.57 | 0.00 | 70.21 | 100 | 33.33 |
| 19 | 50 | 2.3 | 2.3 | 0.5 | 0.53 | 0.95 | 0.95 | 0.37 | 0.58 | 0.00 | 210.64 | 100 | 36.21 |
| 20 | 50 | 2.4 | 2.4 | 0.6 | 0.54 | 0.96 | 0.96 | 0.36 | 0.59 | 0.00 | 175.53 | 100 | 38.98 |
| 21 | 50 | 2.5 | 2.5 | 0.7 | 0.55 | 0.97 | 0.97 | 0.35 | 0.60 | 0.00 | 150.46 | 100 | 41.67 |
| 22 | 50 | 2.6 | 2.6 | 0.8 | 0.56 | 0.98 | 0.98 | 0.34 | 0.40 | 0.00 | 131.65 | 100 | 15.00 |
| 23 | 50 | 2.7 | 2.7 | 0.9 | 0.57 | 0.99 | 0.99 | 0.33 | 0.45 | 0.00 | 117.02 | 100 | 26.67 |
| 24 | 50 | 2.8 | 2.8 | 1 | 0.58 | 1.00 | 1.00 | 0.32 | 0.50 | 0.00 | 105.32 | 100 | 36.00 |
| 25 | 50 | 2.9 | 2.9 | 0.9 | 0.59 | 0.98 | 0.95 | 0.31 | 0.55 | 0.00 | 134.13 | 100 | 43.64 |
| 26 | 50 | 3 | 3 | 0.8 | 0.60 | 0.99 | 0.96 | 0.30 | 0.60 | 0.00 | 165.93 | 100 | 50.00 |
| 27 | 50 | 1.4 | 1.6 | 0.5 | 0.35 | 0.95 | 0.95 | 0.50 | 0.51 | 8.66 | 128.72 | 100 | 1.96 |
| 28 | 50 | 1.5 | 1.7 | 0.6 | 0.36 | 0.96 | 0.96 | 0.49 | 0.52 | 8.51 | 107.27 | 100 | 5.77 |
| 29 | 50 | 1.6 | 1.8 | 0.7 | 0.37 | 0.97 | 0.97 | 0.48 | 0.53 | 8.37 | 91.95 | 100 | 9.43 |
| 30 | 50 | 1.7 | 1.9 | 0.8 | 0.38 | 0.98 | 0.98 | 0.47 | 0.54 | 8.23 | 80.45 | 100 | 12.96 |
| 31 | 50 | 1.8 | 2 | 0.9 | 0.39 | 0.99 | 0.99 | 0.46 | 0.55 | 8.10 | 71.51 | 100 | 16.36 |
| 32 | 50 | 1.9 | 2.1 | 1 | 0.40 | 1.00 | 1.00 | 0.45 | 0.56 | 7.98 | 64.36 | 100 | 19.64 |
| 33 | 50 | 2 | 2.2 | 0.5 | 0.41 | 0.95 | 0.95 | 0.44 | 0.46 | 7.39 | 198.94 | 100 | 4.35 |
| 34 | 50 | 2.1 | 2.3 | 0.6 | 0.42 | 0.96 | 0.96 | 0.43 | 0.47 | 7.29 | 165.78 | 100 | 8.51 |
| 35 | 50 | 2.2 | 2.4 | 0.7 | 0.43 | 0.97 | 0.97 | 0.42 | 0.48 | 7.20 | 142.10 | 100 | 12.50 |
| 36 | 50 | 2.3 | 2.5 | 0.8 | 0.44 | 0.98 | 0.98 | 0.41 | 0.49 | 7.11 | 124.34 | 100 | 16.33 |
| 37 | 50 | 2.4 | 2.6 | 0.9 | 0.45 | 0.99 | 0.99 | 0.40 | 0.50 | 7.02 | 110.52 | 100 | 20.00 |
| 38 | 50 | 2.5 | 2.7 | 1 | 0.46 | 1.00 | 1.00 | 0.39 | 0.51 | 6.94 | 99.47 | 100 | 23.53 |
| 39 | 50 | 2.6 | 2.8 | 0.7 | 0.47 | 0.95 | 0.95 | 0.38 | 0.52 | 6.45 | 175.53 | 100 | 26.92 |
| 40 | 50 | 2.7 | 2.9 | 0.8 | 0.48 | 0.96 | 0.96 | 0.37 | 0.53 | 6.38 | 153.59 | 100 | 30.19 |
| 41 | 50 | 2.8 | 3 | 0.9 | 0.49 | 0.97 | 0.97 | 0.36 | 0.54 | 6.32 | 136.52 | 100 | 33.33 |
Embodiment 1(initial molar ratio
n 1< 1.4, and
n 2when>=1.4, this patent tackiness agent host method prepared by resol).
Preparation method, gets alcohol dissolubility resol 100Kg(
w 1), add 125 Kg(
w 2) stir in ethanol, add 38.98Kg after dissolving, concentration is 35%(
w 1) formalin (
f 1), with the NaOH aqueous solution adjust pH to 9 of 40% concentration, be warming up to 60 DEG C, insulation reaction, to 250mPas, is cooled to 50 DEG C, and adding purity is 95%(
w 3) 105.32Kg Resorcinol (
p 2), be incubated and react viscosity 500 mPas to terminal at 50 DEG C, storage at lower temperature.
Embodiment 2-9, preparation method is identical with embodiment 1 except raw material dosage.
Embodiment 10(initial molar ratio
n 1>=1.4, and
n 1=
n 2time resol prepare this patent tackiness agent host method).
Preparation method, water-soluble resol 100Kg(
w 1) stir, vacuumize 6.12 Kg(
w 2) water, with the NaOH aqueous solution adjust pH to 10 of 40% concentration, be warming up to 70 DEG C, insulation reaction, to 250mPas, is cooled to 50 DEG C, and adding purity is 98%(
w 3) 43.88Kg Resorcinol (
p 2), be incubated and react viscosity 500 mPas to terminal at 50 DEG C, storage at lower temperature.
Embodiment 11-26, preparation method is identical with embodiment 10 except raw material dosage.
Embodiment 27(mol ratio>=1.4, and
n 2>
n 1time resol prepare this patent tackiness agent host method).
Preparation method, water-soluble resol 100Kg(
w 1), vacuum deviates from 1.96 Kg(
w 2) water, add 8.66Kg, concentration is 35%(
w 1) formalin (
f 1), with the KOH aqueous solution adjust pH to 11 of 40% concentration, be warming up to 80 DEG C, insulation reaction, to 250mPas, is cooled to 50 DEG C, and adding purity is 95%(
w 3) 128.72Kg Resorcinol (
p 2), be incubated and react viscosity 500 mPas to terminal at 50 DEG C, storage at lower temperature.
Embodiment 28-41, preparation method is identical with embodiment 27 except raw material dosage.
Be described further below in conjunction with the ratio of embodiment to invention adhesive host and solidifying agent, but protection scope of the present invention is not limited to embodiment, the equivalence that related personnel does with technical solution of the present invention changes, and all belongs in scope.
Described timber structure tackiness agent host embodiment mixes with scale, as table 2 with solidifying agent.
Table 2
Test example 1, invention adhesive glue performance is tested.
The present invention is used for GLULAM hot pressing or cold pressure test, wood raw material used is Korean pine, and raw materials size is that 100cm × 20cm × 2cm(is long × wide × thick), 10 pieces of plate rift grain assembly room temperature gummeds.The proportioning of tackiness agent host and solidifying agent is in table 2, and unglued Sample detects through national wood-based plate Quality Supervision and Inspection Center, and detected result is in table 3, and detected result all meets GB/T 26899-2011 standard.
Table 3
Test example 2, invention adhesive product performance are tested.
Host embodiment gained tackiness agent is delivered to the test of national wood-based plate quality surveillance inspection center, test result is as table 4.
Table 4
Claims (3)
1. phenolic resin is changed into the method for fast setting timber structure tackiness agent, it is characterized in that: the method comprises following processing step:
1) tackiness agent host preparation;
2) solidifying agent preparation;
3) tackiness agent host, main solidifying agent and extender are the mixing of 100:5-30:5-30 ratio by weight, be formed in hot pressing or fast setting timber structure tackiness agent under condition of colding pressing, described hot pressing is mainly for the following sheet material of assembly thickness 100mm, hot pressing time: 0.5-1min/mm, temperature: 80-140 DEG C, unit pressure: 0.5-1.2MPa, described colds pressing mainly for the above sheet material of assembly thickness 100mm, time: 2-8h, temperature: room temperature; Unit pressure: 0.5-1.2Mpa;
The preparation of described tackiness agent host be with common commercially available or finished product thermoplastic or heat-reactive phenolic resin for raw material, under predetermined pH value and temperature condition, make tackiness agent host with toughener copolymeric condensation;
Described processing step 2) preparation of solidifying agent, comprising:
1) be the formaldehyde solution of more than 35% with mass concentration, with the glyoxal solution of the gauge of dry-matter, concentration more than 40%, with the one in the gauge of dry-matter, paraformaldehyde or hexamethylenetetramine for main solidifying agent;
Described extender, comprises flour, bean powder, potato powder, blood meal, wood powder, tree bark powder, seed hulls powder or straw powder.
2. method phenolic resin being changed into fast setting timber structure tackiness agent as claimed in claim 1, it is characterized in that: described processing step 1) preparation of tackiness agent host be with common commercially available or finished product thermoplastic or heat-reactive phenolic resin for raw material, under predetermined pH value and temperature condition, make tackiness agent host with toughener copolymeric condensation; Described novolac resin refers to that the mol ratio of formaldehyde and phenol is less than or equal to 1, the water-soluble obtained through acid, alkaline or divalent-metal ion catalyst or ethanol-soluble type commercial phenolic resin; Described heat-reactive phenolic resin refers to that the mol ratio of formaldehyde and phenol is greater than 1, the water-soluble obtained through acid, alkaline or divalent-metal ion catalyst or ethanol-soluble type commercial phenolic resin; Described toughener is the Resorcinol of technical grade, Metha Amino Phenon, Phloroglucinol monomethyl ether, 3,5 xylenols, the one in meta-cresol; Described common commercially available or finished thermoplastic or heat-reactive phenolic resin, adopt the mode of dilution or devolatilization fugitive constituent to adjust its solids content at 40-60%; When solids content is greater than 60%, add alcohol or thin up, the addition of ethanol or water is to make the solids content of phenol resin solution between 40-60%, and final solids content is determined according to actual needs; When solids content lower than 40% time then dewater or dealcoholysis, deviate from amount to make the solids content of phenol resin solution between 40-60%, final solids content is determined according to actual needs; Described solids content must add the formalin of mass concentration more than 35% at the novolac resin of 40-60%, and make its mol ratio formaldehyde/phenol >=1.4, formalin addition is depending on final mol ratio or according to actual needs; The heat-reactive phenolic resin of described solids content between 40-60%, as initial molar ratio 1 < formaldehyde/phenol < 1.4, must add the formalin of mass concentration more than 35% and make its mol ratio formaldehyde/phenol >=1.4, formalin addition is depending on final mol ratio or according to actual needs; The heat-reactive phenolic resin of described solids content between 40-60%, its initial molar ratio formaldehyde/phenol >=1.4, then add or do not add the formalin of more than 35% concentration, depending on final mol ratio or according to actual needs; Described solids content is between 40-60%, and the phenol resin solution of final mol ratio formaldehyde/phenol >=1.4 need be that the sodium hydroxide of 30-40% or potassium hydroxide solution adjust ph are at 9-13 by mass concentration; Described solids content at 40-60%, final mol ratio formaldehyde/phenol >=1.4, pH value is at the phenol resin solution of 9-13, and viscosity when its 25 DEG C should between 200-300mPas; Viscosity < 200mPas when 25 DEG C, then temperature reaction, range of reaction temperature, at 50-100 DEG C, makes its viscosity reach 200-300mPas, is then cooled to less than 50 DEG C; Need to add toughener in the phenol resin solution of viscosity between 200-300mPas, toughener refers to the Resorcinol of technical grade, Metha Amino Phenon, Phloroglucinol monomethyl ether, 3,5 xylenols, the one in the aldehydes matters such as meta-cresol, addition drops to 0.5-0.9 with the mol ratio of formaldehyde after making interpolation toughener and total aldehydes matter; And insulation reaction, temperature of reaction remains on less than 60 DEG C, when reaction end viscosity controller is between 300-500mPas, is cooled to room temperature storage; Make the host of tackiness agent thus.
3. method phenolic resin being changed into fast setting timber structure tackiness agent as claimed in claim 1, it is characterized in that: main solidifying agent to be mass concentration be more than 35% formaldehyde solution, concentration be more than 40% glyoxal solution be with dry-matter gauge, paraformaldehyde is ground to more than 200 orders, and hexamethylenetetramine is ground to more than 200 orders; Extender comprises flour, bean powder, potato powder, blood meal, wood powder, tree bark powder, seed hulls powder or straw powder, is all crushed to more than 100 orders.
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