CN103865018B - A kind of matrix resin and a kind of structure laminated wood stick with glue agent - Google Patents
A kind of matrix resin and a kind of structure laminated wood stick with glue agent Download PDFInfo
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- CN103865018B CN103865018B CN201410140024.7A CN201410140024A CN103865018B CN 103865018 B CN103865018 B CN 103865018B CN 201410140024 A CN201410140024 A CN 201410140024A CN 103865018 B CN103865018 B CN 103865018B
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- resorcinol
- formaldehyde
- phenol
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- matrix resin
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 76
- 239000003292 glue Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 24
- 239000011159 matrix material Substances 0.000 title claims abstract description 18
- 239000002023 wood Substances 0.000 title claims abstract description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 108
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 96
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 3
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000007711 solidification Methods 0.000 abstract description 13
- 230000008023 solidification Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 10
- 229920001568 phenolic resin Polymers 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 9
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- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 22
- 238000012360 testing method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 8
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- 238000010008 shearing Methods 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 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 6
- 239000000463 material Substances 0.000 description 5
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- 229920003987 resole Polymers 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 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 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 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
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
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Abstract
The invention belongs to field of adhesive technology, be specifically related to a kind of matrix resin and a kind of structure laminated wood sticks with glue agent.This matrix resin is prepared from by Resorcinol, phenol, formaldehyde, and mol ratio is: Resorcinol: phenol: formaldehyde=(0.1-0.45): 1:(0.9-1.7).Described tackiness agent is prepared by following methods: after phenol and formaldehyde being mixed in proportion, adjust ph is to 9-11, at 70 DEG C-90 DEG C reaction 0.5-1.5 hour, add the Resorcinol of specified amount when then reducing the temperature to 50 DEG C-70 DEG C in batches, react 1-3 hour to obtain matrix resin, then add solidifying agent and other auxiliary agents.This tackiness agent ambient temperature curable, the high strength bond of implementation structure laminated wood.With resorcinol formaldehyde (RF) resin-phase ratio, there is the advantage that cost is low, cohesive strength is high; With phenol formaldehyde (PF) (PF) resin-phase than having the low advantage of solidification value.
Description
Technical field
The present invention relates to field of adhesive technology, specifically disclose a kind of matrix resin and a kind of tackiness agent for structure laminated wood.
Background technology
Structure laminated wood, as the term suggests, be take timber as raw material, by compression set make can as the engineering post material of load larrying member or crossbeam.Will inevitably use tackiness agent in gummed pressing process, this type of tackiness agent is commonly referred to as timber work glue.With traditional riveting, weldering, nail, the methods of attachment such as screw thread are compared, and gummed has the advantages such as good looking appearance, lightweight, intensity is high, stress distribution is even, is therefore widely used in Modern Wood house and the timber buildings such as wooden bridge beam and wood pagoda frame.
In China, timber work glue accounts for more than 70% of tackiness agent ultimate production, and current timber work glue is widely used mainly contains urea-formaldehyde resin adhesive, Phenol aldehyde resin and melamine-formaldehyde resin adhesive.Each tackiness agent varieties and characteristics determines its market purposes.Wherein the water tolerance of urea-formaldehyde resin adhesive and ageing resistance poor, so it is generally used for indoor; Melamine-formaldehyde resin adhesive due to fragility large, the more high reason of price, makes its application scenario in the industrial production and few; Phenol aldehyde resin is easy to get due to raw material, and antifatigue, resistance to boiling water and noncorrosive all kinds of SOLVENTS are good, therefore usually for outdoor.
But the glue-line color of Phenol aldehyde resin is dark, and particularly hot pressing temperature is high, set time is long, makes it receive certain restriction in laminated structure engineering material.In order to reduce solidification value and the time not too affects its performance again, usually introducing properties-correcting agent Resorcinol and modification is carried out to it.The bonding strength of the resorcinol phenol formaldehyde resin glue obtained is higher than GB/T50708-2012 and cost is lower, solidification value is low.
The people such as Tao Yubo (forest product industry, 2005,32 (1): 13-16) are with urea, phenol, formaldehyde for raw material, and adopt rational technique urea to carry out modification to resol, the curing speed of obtained resol is improved.The hot pressing time of urea-modified phenolic glue shaving board can shorten 35% than common phenolic glue shaving board, and when to substitute phenol amount be 25%-30% to urea, the cost of synthetic adhesive can reduce 15%-20%.The people such as Lie group (Sichuan Union University journal, 1998,2 (3): 42-47) make the product obtained maintain the advantage of original good heat resistance with tung oil to phenolic resin modified method, improve original hard fragility simultaneously.This grade of official Du (forest-science, 2000,36(5): 73-77) with the condensation copolymerization resin of phenol, urea, formaldehyde synthesis, shelf-stable, show that the thermal behavior of phenol-urea-formaldehyde condensation copolymerization resin is quite similar from resol and significantly different with urea-formaldehyde resin through differential thermal analysis and thermogravimetric analysis, but curing speed is faster than resol.Yang (JournalofAppliedPolymerScience, 1990,41:1327), with a certain amount of formaldehyde, processes polymeric amide, can obtain methylol polymeric amide in certain temperature and certain hour.This polymeric amide solubility property is good, and adhesion property is high, with-the CH of resol
2oH radical reaction solidifies, and can obtain good cohesive strength.
Yu Hongwei etc. (CN101544878A) with in the alkali lignin oxidized starch modified phenolic glue normal temperature obtained storage period > 2 months, there are sedimentation time > 20 days, its bonding strength > 0.8MPa of boiling water boiling 2h, average burst size of methanal 0.45mg/L, reaches E0 level.Cao your pupils etc. (CN102732196A) have invented the environmental friendly, anti-corrosive mildew-resistant aldehyde glue obtained by bisphenol A modified phenolic glue, Antisepticize and mildew preventive, dispersant, be applicable to bamboo and wood tackiness agent, especially the tackiness agent making Restruction bamboo timber is suitable for, there is free phenol and free aldehyde burst size is low, anticorrosion, mildew-resistant, vermins-proof effect are good, the advantage that solidification value is low and moisture resistance is good.
(chemistry of forest product and the industry such as Wang Chunpeng, 1999,19(4): 23-28) adopt Resorcinol, phenol, formaldehyde to be raw material, under high temperature (104 DEG C), the mol ratio of Resorcinol, phenol, formaldehyde is 0.6:1:(1-1.5) react 3 hours, the wet tenacity of goods is 1.7-7.0MPa.But the Resorcinol amount used in such scheme is large, and temperature of reaction is higher, and the glue cost thus prepared is high, is difficult to realize suitability for industrialized production.
Summary of the invention
The object of the invention is to make up the deficiencies in the prior art, for market provides a kind of matrix resin and a kind of tackiness agent for structure laminated wood, by the improvement to formula and preparation method, under the prerequisite meeting " laminated structure technical specifications " national standard, reduce the consumption of Resorcinol, lower temperature of reaction, thus reduce costs, realize self-vulcanizing simultaneously and shorten set time.
For achieving the above object, technical scheme of the present invention is:
A kind of matrix resin, be prepared from by Resorcinol, phenol and formaldehyde, the mol ratio of described Resorcinol, phenol and formaldehyde is: Resorcinol: phenol: formaldehyde=(0.1-0.45): 1:(0.9-1.7); Concrete preparation method is: after first phenol and formaldehyde being mixed in described ratio, adjust ph is to 9-11, at 70 DEG C-90 DEG C reaction 0.5-1.5 hour, the Resorcinol of 30%-50% specified amount is added when then reducing the temperature to 50 DEG C-70 DEG C, reaction 1-3 hour, add remaining Resorcinol again, continue reaction and obtain matrix resin in 1-3 hour.
Consider from cost-saving angle, the mol ratio of described Resorcinol, phenol and formaldehyde is preferably: Resorcinol: phenol: formaldehyde=(0.25-0.35): 1:(0.9-1.7).
A kind of structure laminated wood sticks with glue agent, is mixed by above-mentioned matrix resin and solidifying agent and weighting agent; Described hardener dose is matrix resin quality consumption 2%-20%; Filler loading is matrix resin quality consumption 0.5%-10%.
One or more preferably in hexamethylenetetramine, paraformaldehyde, trimeric cyanamide of described solidifying agent.More preferably paraformaldehyde.
Described solidifying agent is preferably the solidifying agent after ground 120-180 mesh sieve.
Described weighting agent be preferably metal hydrate, wood fibre, bean powder, starch one or more.
Preferably use solid alkali pH value to 9-11, described solid alkali be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood any one.
Below the present invention be further explained and illustrate:
The composition of resorcinol phenol formaldehyde resin collagen material of the present invention is Resorcinol, phenol, formaldehyde mole ratio be (0.1-0.45): 1:(0.9-1.7).In the raw material preparing resorcinol phenol formaldehyde resin tackiness agent, Resorcinol price is the highest, and phenol price is placed in the middle, and formaldehyde price is minimum.Therefore the conference of Resorcinol consumption causes the manufacturing cost of glue to increase, but content is too low, and the solidification value of glue can be made to improve, and not exclusively, set time is long at room temperature solidification.The low meeting of formaldehyde content consumption makes the adhesive property of glue decline, but the too high meeting of formaldehyde consumption makes glue Free-formaldehyde amount increase and bring environmental issue.Therefore by improve in synthesis technique Resorcinol consumption and formaldehyde consumption to reducing costs, to alleviate environmental pollution significant.
The present invention adopt Resorcinol in batches feed postition replace once adding the mode of Resorcinol, successful, dry strength and wet tenacity all significantly improve.
In preparation method of the present invention, temperature is lower than ordinary method, and temperature of reaction is reduced to about 65 DEG C reactions from 104 DEG C of bibliographical information, and energy consumption reduces successful.In the application, the pH value of temperature and reaction system controls very crucial, and only at suitable temperature and pH value, the tackiness agent of preparation is used for laminated product, just has desirable shearing resistance.
Our product strength 7.6-8.5MPa is higher than background document 7.0MPa, and do not promote shearing resistance in background document, this is the prior index of specific humidity shearing resistance, and the dry shearing resistance that we obtain product exceedes national standard 40%(the application 14.9MPa, GB standard 10.0MPa)
In the present invention, sodium hydroxide adds in mixed solution in solid form, because the membership that adds of sodium hydroxide makes mixeding liquid temperature raise, therefore slowly should add in actually operating, prevent due to the sharply rising of mixeding liquid temperature and bring danger.
In order to accelerate the curing speed of tackiness agent, shortening set time, adding a certain amount of solidifying agent before applying glue of being everlasting in resin, the solidifying agent that can be used as resorcinol phenol formaldehyde resin has hexamethylenetetramine, paraformaldehyde, trimeric cyanamide etc.The solidification effect studying known paraformaldehyde is by experiment best.The solidification effect impact of solidifying agent on tackiness agent is very large, and within identical set time, the shearing resistance adding the adhesive glue combination product of solidifying agent significantly improves.
Paraformaldehyde, as a kind of solidifying agent, has not been catalysis, but a kind of crosslinked action.Paraformaldehyde depolymerization speed is at low temperatures comparatively slow, along with the rising depolymerization speed of temperature is accelerated.So it should add before gluing.In order to make paraformaldehyde and mixed with resin evenly, be usually crushed to 80-200 order.Must stir after adding solidifying agent in resin and can use.
In order to reduce the shrinking percentage in adhesive solidification process, playing thickening power simultaneously, avoiding glue to cause starved because flowing in the curing process.The application can add appropriate weighting agent to improve the mechanical property of tackiness agent and to reduce the cost of product according to the physicals of tackiness agent.Can be used as the weighting agent of resorcinol phenol formaldehyde resin glue has one or more of superfine metal hydrate, wood fibre, bean powder, starch composite.
Resorcinol phenol formaldehyde resin glue of the present invention is mainly used in outdoor use timber engineering material.During use, this RPF resin is evenly applied bonded material surface adhesion by automatization continuous forming machine or batch process route, Amount of spread is 150-200g/m
2.By GB/T50708-2012 standard testing, test result is all higher than national standard.
Compared with prior art, the advantage of the application is:
1, obviously reduce Resorcinol consumption, the price of Resorcinol is about 3-4 times of phenol price, is reaching under identical or better cohesive strength, reduces Resorcinol consumption and greatly can reduce production cost.
2, significantly reduce temperature of reaction, be reduced to about 65 DEG C from existing more than 100 DEG C, obviously more easily operate, more energy-conservation.
The cohesive strength of the sizing agent 3, prepared by the application is higher than currently available products.
4, the sizing agent solidification value prepared by the application is low, and set time is short.
Embodiment
Below by embodiment, the present invention is described in further detail, feature of the present invention can be become apparent more.But the present invention is in no way limited to these embodiments.
embodiment 1
By formaldehyde solution 73g (concentration 37-40% formaldehyde solution, pH=10.12 is adjusted to down together) and after phenol 85g conjunction with NaOH, 1h is reacted at 90 DEG C, then add Resorcinol 16.5g after being cooled to 65 DEG C and react 1.5h, and then add Resorcinol 16.5g copolycondensation 1.5h, be cooled to 30-40 DEG C, discharging.Add solidifying agent 12g and weighting agent 4g, 30 DEG C of cure under pressures, 5 hours set times, by GB/T50708-2012 standard testing, dry strength is 14.3MPa, and wet tenacity is 7.6MPa.(Resorcinol in reaction system: phenol: the mol ratio of formaldehyde is 0.33:1:1.04)
embodiment 2
Be adjusted to pH=10.12 with NaOH after being closed by formaldehyde solution 90g and phenol 85g, at 90 DEG C, react 1h, add Resorcinol 16.5g after being then cooled to 65 DEG C and react 1.5h, and then add Resorcinol 16.5g copolycondensation 1.5h, be cooled to 30-40 DEG C, discharging.Add solidifying agent 12g and weighting agent 4g, 30 DEG C of cure under pressures, 5 hours set times, by GB/T50708-2012 standard testing, dry strength is 14.9MPa, and wet tenacity is 7.5MPa.(Resorcinol in reaction system: phenol: the mol ratio of formaldehyde is 0.33:1:1.28)
embodiment 3
Be adjusted to pH=10.12 with NaOH after being closed by formaldehyde solution 90g and phenol 85g, at 90 DEG C, react 1h, add Resorcinol 16.5g after being then cooled to 65 DEG C and react 1.5h, and then add Resorcinol 16.5g copolycondensation 2h, be cooled to 30-40 DEG C, discharging.Add solidifying agent 12g and weighting agent 4g, 30 DEG C of cure under pressures, 5 hours set times, by GB/T50708-2012 standard testing, dry strength is 13.9MPa, and wet tenacity is 7.4MPa.(Resorcinol: phenol: the mol ratio of formaldehyde is 0.33:1:1.28)
embodiment 4
Concrete steps, with embodiment 1, are Resorcinol: phenol: the mol ratio of formaldehyde is 0.15:1:1.28, products obtained therefrom, by GB/T50708-2012 standard testing, dry strength is 13.6MPa, and wet tenacity is 7.3MPa.
embodiment 5
Concrete steps, with embodiment 1, are Resorcinol: phenol: the mol ratio of formaldehyde is 0.43:1:1.28, products obtained therefrom, by GB/T50708-2012 standard testing, dry strength is 15.5MPa, and wet tenacity is 8.4MPa.
comparative example 1
Be adjusted to pH=10.12 with NaOH after being mixed by formaldehyde solution 90g and phenol 85g, at 90 DEG C, react 1h, add Resorcinol 4.5g after being then cooled to 65 DEG C and react 1.5h, and then add Resorcinol 4.5g copolycondensation 1.5h, be cooled to 30-40 DEG C, discharging.Add solidifying agent 10g and weighting agent 3g, 30 DEG C of cure under pressures, 10 hours set times, by GB/T50708-2012 standard testing, dry strength is 10.8MPa, and wet tenacity is 4.1MPa.
Resorcinol in this reaction system: phenol: the mol ratio of formaldehyde is 0.09:1:1.28, shows that in reaction system, Resorcinol is very few, will make extend set time, and not exclusively, wet shearing resistance does not reach Standard in solidification.
comparative example 2
Be adjusted to pH=10.12 with NaOH after being mixed by formaldehyde solution 90g and phenol 85g, at 90 DEG C, react 1h, add Resorcinol 9.0g after being then cooled to 65 DEG C and react 3.0h, be cooled to 30-40 DEG C, discharging.Add solidifying agent 10g and weighting agent 3g, 30 DEG C of cure under pressures, 10 hours set times, by GB/T50708-2012 standard testing, dry strength is 6.2MPa, and wet tenacity is 3.0MPa.
Outside Resorcinol once adds, other are identical with comparative example 1, once add the glue shear-strength preparing sizing agent and are starkly lower than and add in batches.
comparative example 3
Be adjusted to pH=10.12 with NaOH after being mixed by formaldehyde solution 90g and phenol 85g, at 90 DEG C, react 1h, add Resorcinol 4.5g after being then cooled to 65 DEG C and react 1.5h, and then add Resorcinol 4.5g copolycondensation 1.5h, be cooled to 30-40 DEG C, discharging.Do not add solidifying agent, add weighting agent 3g, 30 DEG C of room temperature cure under pressures, 10 hours set times, by GB/T50708-2012 standard testing, dry strength is 5.6MPa, and wet tenacity is 2.0MPa.
Except not adding except solidifying agent, other are identical with comparative example 1, show that solidifying agent has the effect promoting sizing agent solidification to sizing agent, and when not adding solidifying agent, 10 hours set times, not exclusively, dry strength and wet tenacity are all lower than comparative example 1 in solidification.
comparative example 4
Be adjusted to pH=10.12 with NaOH after being closed by formaldehyde solution 73g () and phenol 85g, at 90 DEG C, react 1h, add Resorcinol 33g after being then cooled to 65 DEG C and react 3.0h, be cooled to 30-40 DEG C, discharging.Add solidifying agent 12g and weighting agent 4g, 30 DEG C of cure under pressures, 5 hours set times, by GB/T50708-2012 standard testing, dry strength is 10.8MPa, and wet tenacity is 5.2MPa.
Except Resorcinol once adds, other are identical with embodiment 1, show once to add the glue shear-strength preparing sizing agent and are starkly lower than and add in batches.
comparative example 5
PH=8.5 is adjusted to NaOH after being closed by formaldehyde 73g (concentration 37-40% formaldehyde solution) and phenol 85g, 1h is reacted at 90 DEG C, then add Resorcinol 16.5g after being cooled to 65 DEG C and react 1.5h, and then add Resorcinol 16.5g copolycondensation 1.5h, be cooled to 30-40 DEG C, discharging adds solidifying agent 12g and weighting agent 4g, 30 DEG C of cure under pressures, 5 hours set times, by GB/T50708-2012 standard testing, dry strength is 10.6MPa, and wet tenacity is 5.3MPa.
Outside the pH value of reaction system reduces, other are identical with embodiment 1, show pH value lower than 9 time, dry, the shearing resistance that wets of preparing sizing agent significantly decline.
Claims (7)
1. structure laminated wood sticks with glue an agent, is mixed by matrix resin and solidifying agent and weighting agent; Described hardener dose is matrix resin quality consumption 2%-20%; Filler loading is matrix resin quality consumption 0.5%-10%; Described matrix resin, is prepared from by Resorcinol, phenol and formaldehyde, and wherein the mol ratio of Resorcinol, phenol and formaldehyde is: Resorcinol: phenol: formaldehyde=(0.1-0.45): 1:(0.9-1.7); The preparation method of described matrix resin is: after first phenol and formaldehyde being mixed in described ratio, adjust ph is to 9-11, at 70 DEG C-90 DEG C reaction 0.5-1.5 hour, the Resorcinol of 30%-50% specified amount is added when then reducing the temperature to 50 DEG C-70 DEG C, reaction 1-3 hour, add remaining Resorcinol again, continue reaction and obtain matrix resin in 1-3 hour.
2. structure laminated wood sticks with glue agent according to claim 1, it is characterized in that, described solidifying agent is selected from one or more in hexamethylenetetramine, paraformaldehyde and trimeric cyanamide.
3. according to claim 1 or 2, structure laminated wood sticks with glue agent, it is characterized in that, described solidifying agent is paraformaldehyde.
4. according to claim 1 or 2, structure laminated wood sticks with glue agent, it is characterized in that, described solidifying agent is the solidifying agent after ground 120-180 mesh sieve.
5. according to claim 1 or 2, structure laminated wood sticks with glue agent, it is characterized in that, described weighting agent be metal hydrate, wood fibre, bean powder, starch one or more.
6. according to claim 1 or 2, structure laminated wood sticks with glue agent, it is characterized in that, with solid alkali adjust pH to 9-11, described solid alkali be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood any one.
7. according to claim 1 or 2, structure laminated wood sticks with glue agent, it is characterized in that, the mol ratio of described Resorcinol, phenol and formaldehyde is: Resorcinol: phenol: formaldehyde=(0.25-0.35): 1:(0.9-1.7).
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| CN104877610B (en) * | 2015-05-12 | 2017-06-30 | 中南林业科技大学 | A kind of resorcinol dialdehyde starch formaldehyde condensation copolymerization resin adhesive and preparation method thereof |
| CN105440971B (en) * | 2015-11-30 | 2017-12-05 | 中南林业科技大学 | A kind of curing agent of laminated wood adhesive |
| CN107964080B (en) * | 2016-10-19 | 2020-06-05 | 中南林业科技大学 | Waxberry tannin extract modified phenolic resin and preparation method and application thereof |
| CN107586524B (en) * | 2017-10-23 | 2021-05-18 | 黑龙江省科学院石油化学研究院 | Preparation method of normal-temperature-cured high-temperature-resistant phenolic adhesive |
| CN109456516B (en) * | 2018-11-19 | 2021-03-05 | 北京彤程创展科技有限公司 | Bisphenol compound modified resorcinol resin, rubber composition and preparation method thereof |
| CN110734723A (en) * | 2019-11-08 | 2020-01-31 | 安徽阜南县向发工艺品有限公司 | wood craft strong adhesive and preparation method thereof |
| CN112175155B (en) * | 2020-08-17 | 2022-10-14 | 杭摩新材料集团股份有限公司 | Special phenolic resin for nylon cord fabric and production method thereof |
| CN113845636A (en) * | 2021-11-30 | 2021-12-28 | 苏州艾特斯环保设备有限公司 | Method for synthesizing non-combustible phenolic resin matrix for non-combustible glass fiber reinforced plastics |
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| CN1966587A (en) * | 2005-11-14 | 2007-05-23 | 北京化工大学 | Normal temperature cured phenol resin timber adhesive |
| CN102627927A (en) * | 2012-03-26 | 2012-08-08 | 黑龙江省科学院石油化学研究院 | Medium temperature curing high temperature resistant phenolic adhesive |
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| CN102627927A (en) * | 2012-03-26 | 2012-08-08 | 黑龙江省科学院石油化学研究院 | Medium temperature curing high temperature resistant phenolic adhesive |
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