CN103265674A - Phenol-polyaldehyde prepolymer modified environment-friendly phenolic resin and preparation method thereof - Google Patents
Phenol-polyaldehyde prepolymer modified environment-friendly phenolic resin and preparation method thereof Download PDFInfo
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- CN103265674A CN103265674A CN2013101731495A CN201310173149A CN103265674A CN 103265674 A CN103265674 A CN 103265674A CN 2013101731495 A CN2013101731495 A CN 2013101731495A CN 201310173149 A CN201310173149 A CN 201310173149A CN 103265674 A CN103265674 A CN 103265674A
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- phenol
- prepolymer
- many aldehyde
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- PXBVPGJIANEFEL-ZCXUNETKSA-N C/C(/O)=C(/C(C(c1ccccc1OC)C1=CCCC=C1O)c(cccc1)c1O)\C=C Chemical compound C/C(/O)=C(/C(C(c1ccccc1OC)C1=CCCC=C1O)c(cccc1)c1O)\C=C PXBVPGJIANEFEL-ZCXUNETKSA-N 0.000 description 1
- BZSXRIDPHOGATK-UHFFFAOYSA-N OC(CCCC(c(cccc1)c1O)O)c(cccc1)c1O Chemical compound OC(CCCC(c(cccc1)c1O)O)c(cccc1)c1O BZSXRIDPHOGATK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a phenol-polyaldehyde prepolymer modified environment-friendly phenolic resin and a preparation method thereof. The phenolic resin in the method is prepared from phenol, formaldehyde and a phenol-polyaldehyde prepolymer through catalytic synthesis. The preparation method comprises the following steps: synthesizing the phenol-polyaldehyde prepolymer from a polyaldehyde monomer and phenol at a certain temperature in the presence of a catalyst; and introducing the phenol-polyaldehyde prepolymer into a phenolic resin system. The introduction of the phenol-polyaldehyde prepolymer increases the aldehyde equivalent in the system, and can effectively decrease the free phenol content in the resin; and the replacement of part of the formaldehyde with the polyaldehyde can effectively decrease the free formaldehyde content in the resin. Besides, the long-chain structure of the phenol-polyaldehyde prepolymer can enhance the flexibility of the phenolic resin and reduce the internal stress in the curing process, so that a pressed sheet has favorable adhesion strength and can meet the requirements for Class I waterproof plywood. The phenolic resin prepared by the invention has the advantages of low free phenol/free aldehyde content, simple process and the like, and is applicable to the field of production of functional environment-friendly artificial boards.
Description
Technical field
The present invention relates to environment-friendly type resol of a kind of phenol-many aldehyde prepolymer modification and preparation method thereof, belong to timber sizing agent field.
Background technology
Along with development of Chinese economy, the people improve constantly the requirement of daily life quality, and the forest reserves reduce gradually.Therefore, be that the wood-based plate industry of purpose is developed rapidly to improve the timber rate of utilization, particularly over past ten years, China's wood-based plate annual production remains and surpasses 10% rate of growth.China's wood-based plate output surpassed 2.35 hundred million m in 2011
3, rise in 2012 reaches 2.8 m
3About hundred million.Adapt with the wood-based plate industry is flourish, China's timber industry glue consumption in 2012 surpasses 1,500 ten thousand tons, and wherein the resol consumption is only second to urea-formaldehyde resin, is the second largest sizing agent kind of wood-based plate industry.Compare with urea-formaldehyde resin, phenolic resin adhesive has advantages such as bonding strength height, water-tolerant, fine properties, synthesis technique be simple, is mainly used to production I class water-proof plywood, is widely used at high quality artificial plate production field.Indexs such as resol free phenol, sheet material burst size of methanal, storage period, viscosity are measured according to timber sizing agent and resin method of inspection GB/T 14074-2006 thereof.
But, the high problem of phenolic resin adhesive ubiquity free phenol content.In recent years, the harm of free formaldehyde has been subjected to paying attention to widely in the room air, but free phenol is often out in the cold.Be different from the tangible irritating smell of formaldehyde, a certain amount of phenol is not easy to be discovered in air, but phenol belongs to the hypertoxic type material, has strong corrodibility, and contactee's life security is constituted a serious threat.After free phenol in the resol evaporate in the air, enter human body and cause poisoning by respiratory tract and skin, be the cytoplasm poisonous substance, the lower concentration phenol solution can make protein denaturation, cause protein precipitation during high density, cell there is direct infringement, can corrode mucous membrane, infringement cardiovascular systems, suppress nervus centralis, very big to human body harm, the environment-friendly type resol of therefore low free phenol content is an important development direction in following sizing agent field, and improving of its preparation method will bring huge economic benefit and social benefit.
Tradition reduces resol free phenol content and mainly contains two methods: the one, reduce the mol ratio of phenol, formaldehyde, and reduce free phenol but increase the formaldehyde consumption, then free formaldehyde content must raise, and the same health risk of formaldehyde, so this method is inadvisable.The 2nd, substitute phenol with the material part that contains phenolic hydroxyl structure.Use phenol surrogate such as tannin, protein, xylogen etc., but tannin, protein is on the high side, lignin reaction is active lowly can to have a strong impact on the resol performance, so existing phenol surrogate does not have industrial prospect.Therefore new approach be must seek and free phenol content, synthetic environment-friendly phenolic resin adhesive reduced.
Summary of the invention
Environment-friendly type resol of a kind of phenol-many aldehyde prepolymer modification and preparation method thereof, resol in this method by phenol, formaldehyde, phenol-many aldehyde prepolymer by catalyzing and synthesizing, at first synthetic phenol-many aldehyde prepolymer under certain temperature and catalyzer condition by many aldehyde monomer and phenol is introduced in the phenolic resin system then.
The environment-friendly type resol of a kind of phenol-many aldehyde prepolymer modification is characterized in that: comprise phenol, formaldehyde, phenol-many aldehyde prepolymer, basic catalyst, properties-correcting agent; Wherein phenol 47 weight parts, mass percent are 37% formalin: 81-162 weight part, phenol-many aldehyde prepolymer 23-84 weight part, basic catalyst 1-4 part, properties-correcting agent 3-10 weight part; Described phenol-many aldehyde prepolymer is under whipped state the phenol of 47 weight parts, the catalyzer of 0.5-3 weight part to be added reactor, be warming up to 90-120 ℃, dropwise add many aldehyde monomer of 22-62.5 weight part, insulation 2-4h, add 0.5-2 weight part stablizer, cooling discharging obtains.
It is that mass percent is that 40% glyoxal water solution, mass percent are one of glutaraldehyde water solution of 40% that phenol-many aldehyde prepolymer prepares used many aldehyde monomer.It is one of oxalic acid solid, aqueous formic acid, aqueous acetic acid that phenol-many aldehyde prepolymer prepares used catalyzer; It is sodium hydroxide or potassium hydroxide that phenol-many aldehyde prepolymer prepares used stablizer.
The structural formula of phenol-many aldehyde prepolymer is
Or
Basic catalyst is sodium hydroxide, ammoniacal liquor or hydrated barta.
Properties-correcting agent is one of trimeric cyanamide, urea, sodium lignosulfonate.
The preparation method of the environment-friendly type resol of described phenol-many aldehyde prepolymer modification is characterized in that step is as follows:
1) under the state that stirs the phenol of 47 weight parts, the basic catalyst of 1-4 weight part are added reactor, 45-70 ℃ is incubated 10-30min down;
2) formaldehyde solution of adding 81-162 weight part, insulation reaction 30-60min;
3) add phenol-many aldehyde prepolymer, insulation reaction 60min;
4) be warming up to 94 ℃, insulation reaction 60-120min makes viscosity reach 400-1000cp, adds properties-correcting agent 3-10 weight part, cooling discharging, and viscosity is measured according to timber sizing agent and resin method of inspection GB/T 14074-2006 thereof.
The introducing of phenol-many aldehyde prepolymer has increased the aldehyde equivalent in the system, can effectively reduce the free phenol content of resin, and the alternative part formaldehyde of many aldehyde can reduce the free formaldehyde content in the resin effectively simultaneously.In addition, the phenol-backbone of many aldehyde prepolymer can improve the snappiness of resol, reduces the internal stress in its solidification process, makes pressed sheet have good bonding strength, can reach the requirement of I class water-proof plywood.Advantages such as the resol of the present invention's preparation has free phenol, content of free aldehyde is low, and technology is simple are applicable to functional type environment friendly artificial board production field.
Description of drawings
Fig. 1 oxalic dialdehyde-phenol prepolymer
13C NMR spectrogram.
Fig. 2 oxalic dialdehyde modified phenolic resins
13C NMR spectrogram
Fig. 3 oxalic dialdehyde modified phenolic resins
13The local spectrogram that amplifies of C NMR
The 13C NMR spectrogram of Fig. 4 glutaraldehyde-phenol prepolymer
The local spectrogram that amplifies of the 13C NMR of Fig. 5 glutaraldehyde-phenol prepolymer
Fig. 6 glutaraldehyde modified phenolic resins 13C NMR spectrogram
Embodiment:
The preparation of phenol-many aldehyde pre-polymer solution: in the 500ml four-hole bottle of reflux condensate device and whipping appts is housed, the phenol that adds 47g, the oxalic acid of 1g, be warming up to 105 ℃, dropwise adding the 36g mass percent is 40% glyoxal solution, insulation 3h adds 1g sodium hydroxide, and cooling discharging obtains pre-polymer solution.
The preparation of resol: in another 500ml four-hole bottle, open reflux condensate device and whipping appts, the phenol that adds 47g, 2g sodium hydroxide, the massfraction that adds 121g under 60 ℃ behind the insulation 20min is 37% formaldehyde solution, add 84g phenol-many aldehyde pre-polymer solution behind the insulation reaction 30min, continue insulation reaction 1h, be warming up to 94 ℃ of insulation 1.5h, add trimeric cyanamide 5g, treat that viscosity reaches 500cp, cooling discharging, phenol and the amount of substance of aldehyde are than 1:1.5 in the present embodiment, and prepolymer accounts for 35% of resol total mass.
Embodiment 2
Add an acidic catalyst oxalic acid 0.5g among the preparation method of present embodiment prepolymer, other are identical with embodiment 1.
Embodiment 3
Add an acidic catalyst oxalic acid 3g among the preparation method of present embodiment prepolymer, other are identical with embodiment 1.
Embodiment 4
An acidic catalyst is 30% aqueous formic acid for the 3g massfraction among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1.
Embodiment 5
An acidic catalyst is 2g Glacial acetic acid solid among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1.
Embodiment 6
Temperature of reaction is 90 ℃ among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1.
Embodiment 7
Temperature of reaction is 120 ℃ among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1
Massfraction is that 40% glyoxal water solution add-on is 22g among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1.
Embodiment 9
Massfraction is that 40% glyoxal water solution add-on is 58g among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1.
Embodiment 10
Dialdehyde is that massfraction is 40% glutaraldehyde water solution add-on 62.5g among the preparation method of present embodiment prepolymer, and other are identical with embodiment 1.
Embodiment 11
Among the preparation method of present embodiment prepolymer, soaking time is 2h, and other are identical with embodiment 1.
Embodiment 12
Among the preparation method of present embodiment prepolymer, soaking time is 4h, and other are identical with embodiment 1.
Embodiment 13
Among the preparation method of present embodiment prepolymer, the stablizer add-on is 0.5g, and other are identical with embodiment 1.
Embodiment 14
Among the preparation method of present embodiment prepolymer, the stablizer add-on is 2g, and other are identical with embodiment 1.
Embodiment 15
Among the preparation method of present embodiment prepolymer, stablizer is 1g potassium hydroxide solid, and other are identical with embodiment 1.
Embodiment 16
Among the preparation method of present embodiment resol, the basic catalyst add-on is 1g, and other are identical with embodiment 1.
Embodiment 17
Among the preparation method of present embodiment resol, the basic catalyst add-on is 4g, and other are identical with embodiment 1.
Embodiment 18
Among the preparation method of present embodiment resol, basic catalyst is 25% ammonia aqueous solution for the 4g massfraction, and other are identical with embodiment 1.
Embodiment 19
Among the preparation method of present embodiment resol, basic catalyst is 1g hydrated barta solid, and other are identical with embodiment 1.
Embodiment 20
Among the preparation method of this experiment method resol, initial holding temperature is 45 ℃, and other are identical with embodiment 1.
Embodiment 21
Among the preparation method of this experiment method resol, initial holding temperature is 70 ℃, and other are identical with embodiment 1.
Embodiment 22
Among the preparation method of this experiment method resol, soaking time is 10min, and other are identical with embodiment 1.
Embodiment 23
Among the preparation method of this experiment method resol, soaking time is 30min, and other are identical with embodiment 1.
Embodiment 24
Among the preparation method of present embodiment resol, the formalin add-on of massfraction 37% is 91g, and prepolymer aqueous solution add-on is 45g, and namely the prepolymer quality accounts for 25% of resol total amount, and other are identical with embodiment 1.
Embodiment 25
Among the preparation method of present embodiment resol, the formalin add-on of massfraction 37% is 83g, and prepolymer aqueous solution add-on is 23g, and namely the prepolymer quality accounts for 15% of resol total amount, and other are identical with embodiment 1.
Embodiment 26
Among the preparation method of present embodiment resol, the formalin add-on of massfraction 37% is 162g, and the mol ratio of phenol and aldehyde is 1:2.0, and other are identical with embodiment 1.
Embodiment 27
Among the preparation method of present embodiment resol, the formalin add-on of massfraction 37% is 81g, and the mol ratio of phenol and aldehyde is 1:1.0, and other are identical with embodiment 1.
Embodiment 28
Among the preparation method of present embodiment resol, do not add properties-correcting agent, other are identical with embodiment 1.
Embodiment 29
Among the preparation method of present embodiment resol, properties-correcting agent trimeric cyanamide add-on is 3g, and other are identical with embodiment 1.
Embodiment 30
Among the preparation method of present embodiment resol, properties-correcting agent trimeric cyanamide add-on is 10g, and other are identical with embodiment 1.
Embodiment 31
Among the preparation method of present embodiment resol, properties-correcting agent is the sodium lignosulfonate of 5g, and other are identical with embodiment 1.
Embodiment 32
Among the preparation method of present embodiment resol, the properties-correcting agent agent is the urea of 5g, and other are identical with embodiment 1.
Embodiment 33
Among the preparation method of present embodiment resol, viscosity is 400cp, and other are identical with embodiment 1.
Embodiment 34
Among the preparation method of present embodiment resol, viscosity is 1000cp, and other are identical with embodiment 1.
Comparative Examples 1
Among the present embodiment resol preparation method, synthetic and adding prepolymer, the phenol add-on is 94g, and the formalin add-on of massfraction 37% is 162g, and other are identical with embodiment 1, obtain the resol that phenol and formaldehyde mole ratio are 1:2.0.
Comparative Examples 2
Among the present embodiment resol preparation method, synthetic and adding prepolymer, the phenol add-on is 94g, and the formalin add-on of massfraction 37% is 120g, and other are identical with embodiment 1, obtain the resol that phenol and formaldehyde mole ratio are 1:1.5.
Comparative Examples 3
Among the present embodiment resol preparation method, synthetic and adding prepolymer, the phenol add-on is 94g, and the formalin add-on of massfraction 37% is 81g, and other are identical with embodiment 1, obtain the resol that phenol and formaldehyde mole ratio are 1:1.0.
Phenol, oxalic dialdehyde reaction equation in the resin building-up process:
Phenol, glutaraldehyde reaction equation in the resin building-up process:
Oxalic dialdehyde among Fig. 1-phenol prepolymer
13C NMR spectrum analysis
Oxalic dialdehyde modified phenolic resins among Fig. 2 and Fig. 3
13C NMR spectrum analysis
Phenol among Fig. 4 and Fig. 5-glutaraldehyde prepolymer 13C NMR spectrum analysis
Glutaraldehyde modified phenolic resins 13C NMR spectrum analysis among Fig. 6
Claims (8)
1. the environment-friendly type resol of phenol-many aldehyde prepolymer modification is characterized in that: comprise phenol, formaldehyde, phenol-many aldehyde prepolymer, basic catalyst, properties-correcting agent; Wherein phenol 47 weight parts, mass percent are 37% formalin: 81-162 weight part, phenol-many aldehyde prepolymer 23-84 weight part, basic catalyst 1-4 part, properties-correcting agent 3-10 weight part; Described phenol-many aldehyde prepolymer is under whipped state the phenol of 47 weight parts, the catalyzer of 0.5-3 weight part to be added reactor, be warming up to 90-120 ℃, dropwise add many aldehyde monomer of 22-62.5 weight part, insulation 2-4h, add 0.5-2 weight part stablizer, cooling discharging obtains.
2. the environment-friendly type resol of a kind of phenol according to claim 1-many aldehyde prepolymer modification is characterized in that: it is that mass percent is that 40% glyoxal water solution, mass percent are one of glutaraldehyde water solution of 40% that phenol-many aldehyde prepolymer prepares used many aldehyde monomer.
3. the environment-friendly type resol of a kind of phenol according to claim 1 and 2-many aldehyde prepolymer modification, it is characterized in that: the structural formula of phenol-many aldehyde prepolymer is
Or
4. the environment-friendly type resol of a kind of phenol according to claim 1-many aldehyde prepolymer modification, it is characterized in that: it is one of oxalic acid solid, aqueous formic acid, aqueous acetic acid that phenol-many aldehyde prepolymer prepares used catalyzer.
5. the environment-friendly type resol of a kind of phenol according to claim 1-many aldehyde prepolymer modification, it is characterized in that: it is sodium hydroxide or potassium hydroxide that phenol-many aldehyde prepolymer prepares used stablizer.
6. the environment-friendly type resol of a kind of phenol according to claim 1-many aldehyde prepolymer modification, it is characterized in that: basic catalyst is sodium hydroxide, ammoniacal liquor or hydrated barta.
7. the environment-friendly type resol of a kind of phenol according to claim 1-many aldehyde prepolymer modification, it is characterized in that: properties-correcting agent is one of trimeric cyanamide, urea, sodium lignosulfonate.
8. according to the preparation method of the environment-friendly type resol of any described phenol of claim 1-7-many aldehyde prepolymer modification, it is characterized in that step is as follows:
1) under the state that stirs the phenol of 47 weight parts, the basic catalyst of 1-4 weight part are added reactor, 45-70 ℃ is incubated 10-30min down;
2) formaldehyde solution of adding 81-162 weight part, insulation reaction 30-60min;
3) add phenol-many aldehyde prepolymer, insulation reaction 60min;
4) be warming up to 94 ℃, insulation reaction 60-120min makes viscosity reach 400-1000cp, adds properties-correcting agent 3-10 weight part, cooling discharging, and viscosity is measured according to timber sizing agent and resin method of inspection GB/T 14074-2006 thereof.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131517A (en) * | 2015-07-16 | 2015-12-09 | 浙江杭摩合成材料有限公司 | Modified thermoplastic phenolic resin adhesive used in automobile brake pad and preparation method thereof |
| CN110240724A (en) * | 2018-03-08 | 2019-09-17 | 欣岱实业股份有限公司 | The application method of reactive polymer phenolic resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358120A (en) * | 2008-09-18 | 2009-02-04 | 华南理工大学 | Environment-friendly type alkali lignin modified phenolic resin adhesive and preparation method thereof |
| CN101602838A (en) * | 2009-07-10 | 2009-12-16 | 北京林业大学 | A kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate |
-
2013
- 2013-05-11 CN CN201310173149.5A patent/CN103265674B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358120A (en) * | 2008-09-18 | 2009-02-04 | 华南理工大学 | Environment-friendly type alkali lignin modified phenolic resin adhesive and preparation method thereof |
| CN101602838A (en) * | 2009-07-10 | 2009-12-16 | 北京林业大学 | A kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate |
Non-Patent Citations (1)
| Title |
|---|
| 囤宏志等: "戊二醛改性酚醛树脂及对泡沫塑料性能的研究", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131517A (en) * | 2015-07-16 | 2015-12-09 | 浙江杭摩合成材料有限公司 | Modified thermoplastic phenolic resin adhesive used in automobile brake pad and preparation method thereof |
| CN110240724A (en) * | 2018-03-08 | 2019-09-17 | 欣岱实业股份有限公司 | The application method of reactive polymer phenolic resin |
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