CN106674456A - Preparation method of modified phenolic resin - Google Patents
Preparation method of modified phenolic resin Download PDFInfo
- Publication number
- CN106674456A CN106674456A CN201611271486.8A CN201611271486A CN106674456A CN 106674456 A CN106674456 A CN 106674456A CN 201611271486 A CN201611271486 A CN 201611271486A CN 106674456 A CN106674456 A CN 106674456A
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- China
- Prior art keywords
- heavy phase
- dimethylbenzene
- phenol
- quality
- preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
Abstract
The invention discloses a preparation method of modified phenolic resin. The method comprises the steps of weighing a heavy phase, polyformaldehyde, urotropine, ethidene diamine and dimethylbenzene according to the material ratio, adding the heavy phase to a reaction container and heating urotropine, ethidene diamine and 30-70% dimethylbenzene to 50-60 DEG C; adding polyformaldehyde in 2-5 batches, heating the raw materials to 85-95 DEG C, carrying out heat preservation for 0.5-2 hours, carrying out heating and dewatering until the temperature is 100-110 DEG C; carrying out dewatering under the condition that the vacuum degree is 0.05-0.1MPa and keeping under the condition of 120-130 DEG C for 20-40 minutes; and adding the balance of dimethylbenzene, stirring evenly, filtering and discharging the materials to obtain the modified phenolic resin. The preparation method is renewable pure plant extraction, and environmentally friendly, and can be applied to the phenolic resin instead of a petroleum extract phenol.
Description
Technical field
The present invention relates to chemical field, more particularly to phenolic resin, a kind of specifically preparation of phenol-formaldehyde resin modified
Method.
Background technology
Phenol-formaldehyde resin modified is (as copolymerization or machinery are mixed with different compound or polymer by chemically or physically method
Close) modified obtained phenolic resin, including polyamide modified phenolic resin, dicyandiamide modified phenolic resin, epoxide modified phenolic aldehyde
Resin, Pioloform, polyvinyl acetal phenol-formaldehyde resin modified etc..It is modified, it is the impact flexibility of phenolic resin, cementability, mechanical strength, resistance to
Hot, anti-flammability, dimensional stability, curing rate, moulded manufacturability etc., respectively obtain raising.Therefore, can be according to actual use
On the way, different phenol-formaldehyde resin modifieds are selected.Through with the effect such as Colophonium, drying oil and fatty acid and change the phenolic aldehyde tree of property
Fat.Can make from original less soluble or be changed into readily soluble or solvable insoluble in vegetable oil or alcohol, be mostly amber solid.It is main to use
In coating processed, ink and adhesive etc..1. the principle of phenol-formaldehyde resin modified has block phenolic hydroxyl group.The phenolic hydroxyl group of phenolic resin is in tree
Typically chemical reaction is not participated in fat manufacture process.The phenolic hydroxyl group stayed in molecular resin chain easily absorbs water, and makes cured article
Electrical property, alkali resistance and mechanical properties decrease.Simultaneously phenolic hydroxyl group easily generates quinone or other structures under heat or action of ultraviolet light,
Cause the uneven change of color.2. other components are introduced.Introduce with phenolic resin occur chemical reaction or with its compatibility compared with
Good component, separates or surrounds hydroxyl, so as to reach change curing rate, reduces absorptive purpose.Introduce other high scores
Subgroup point, then can have the advantage of two kinds of macromolecular materials concurrently.
It is often referred to liquid or solid product by obtained by phenol or its homologue (such as cresol, xylenol) and formaldehyde effect.
According to raw materials used type, phenol and the proportioning of aldehyde, the type of catalyst it is different, thermoplasticity and the class of thermosetting two can be obtained not
Same resin.Only melt when novolac (-lak) is heated and can not be changed into insoluble and not melt state.But adding firming agent (such as six
Methenamine) after can then be changed into thermosetting, with trifunctional or two sense phenols as raw material, exceed in the consumption (mole) of phenol
Generate under the conditions of the consumption (mole) of aldehyde and acidic catalyst.Thermosetting phenolic resin) be heated after be changed into it is insoluble melt state.Phenol
Urea formaldehyde is acidproof, alkaline-resisting, heat-resisting.
The content of the invention
It is an object of the invention to provide a kind of preparation method of phenol-formaldehyde resin modified, described this phenol-formaldehyde resin modified
Preparation method to solve to prepare the complex process of phenol-formaldehyde resin modified in prior art, the easy technical problem of pollution environment.
The invention provides a kind of preparation method of phenol-formaldehyde resin modified, comprises the steps：
1) heavy phase, polyformaldehyde, hexamethylenamine, ethylenediamine, dimethylbenzene are weighed according to material ratio, described heavy phase and polyformaldehyde
Mol ratio be 1: 1.2-4, the quality of described hexamethylenamine for heavy phase quality 1-4%, the quality of described ethylenediamine is
The 1-4% of heavy phase quality, the quality of described dimethylbenzene is the 20-60% of heavy phase quality；
2) heavy phase, hexamethylenamine, ethylenediamine, 30%~70% dimethylbenzene is added to be heated to 50-60 in reaction vessel
DEG C, point 2~5 batches of addition polyformaldehyde are warming up to 85-95 DEG C after adding, be incubated 0.5~2 hour, heat up and are dehydrated to 100~110
DEG C, it is dehydrated under the conditions of vacuum to 0.05~0.1MPa, then kept for 20~40 minutes under conditions of 120-130 DEG C, plus
Enter the dimethylbenzene of surplus, stir, filtering and discharging obtains phenol-formaldehyde resin modified.
Further, described heavy phase be in 1000Pa, under the conditions of 220~240 DEG C, cashew shell oil distillation extraction Cardanol
During remain distillation substrate, in 300-1000, viscosity is 1952mPas to molecular weight.
When material ratio is calculated, heavy phase is calculated with the mean molecule quantity 600 of mixture.
Specifically, it is many containing cashew acid, Cardanol dimer, Cardanol trimer, Cardanol in described distillation substrate
Aggressiveness or cashew acid.
The structural formula of cashew acid is：
The dimeric structural formula of Cardanol is：
The structural formula of Cardanol trimer is：
The course of reaction of the present invention is as follows：
1) reactive modified phenolic resin of cashew acid：
2) dimeric reactive modified phenolic resin：
3) reactive modified phenolic resin of trimer：
The present invention is raw material using the polymer remained in Cardanol extraction process, can be with reduces cost, and this product
In extracting in pure plant cashew nut shell, environmental protection.Now phenolic resin in the product is all mostly to extract material benzene with oil
Phenol is raw material, and oil is non-renewable resources, and phenol is harmful, so the exploitation of this product, be conducive to resource can
Sustainable development and health.
Present invention is mainly applied to 1. substitute waterproof pitch prill, the asphalt waterproofing time limit is short, and high temperature easily melts, and low temperature easily lumps,
It is aging serious, and not environmentally.The present invention can solve the defect of above waterproof pitch prill, and the present invention's is limited to 5 years in waterproof year, makes
Belong to thermosetting resin with after, temperature is more high more matter is close, will not melt, be low-viscosity (mobile) liquid during low temperature storage, be double-component drip
Clearly, firming agent need to be added when using.2. the fields such as refractory brick are substituted.1600 DEG C -1800 DEG C of high temperature does not burn.
The present invention is compared with prior art, and its technological progress is positive and obvious.The present invention is that renewable pure plant is carried
Take, environmental protection, application of the alternative present oil extract phenol on phenolic resin.Phenol is carried as non-renewable oil
Thing is taken, and because low-molecular-weight is volatile, harmful, this product is high polymer, harmless.By orally in fact
Nontoxic (LD50Oral toxicity ＞ 2000mg/kg rats)
Specific embodiment
In following embodiments, from the flourish synthesis petrochemical industry company limited of Zhenjiang Lee's length, hexamethylenamine is from traditional Chinese medicines for polyformaldehyde
Reagent company limited product is learned, ethylenediamine is given birth to from Gutian chemical products, heavy phase from Anhui Meidong Biomaterials Co., Ltd.
The viscosity of product is the heavy phase resin of 1952mPs.
Embodiment 1
300 grams of heavy phase, 1 gram of hexamethylenamine, 21 grams of polyformaldehyde, 4 grams of ethylenediamine, 30 grams of dimethylbenzene is added in reaction bulb
Heavy phase, hexamethylenamine, ethylenediamine, dimethylbenzene is heated to 50-60 DEG C, is dividedly in some parts polyformaldehyde, and 85-95 DEG C is warming up to after adding,
Insulation 1 hour, heat up dehydration to 105 DEG C or so, then vacuum dehydration gradually steps up vacuum to 0.095MPa, be dehydrated to
120-130 DEG C is kept for 30 minutes or so, adds 50 grams of dimethylbenzene so that the solid content of resin is stirred between 80%~90%
Uniformly, filtering and discharging.Viscosity 1972mPas, admittedly containing 82%, yield 94.18%.
Embodiment 2
300 grams of heavy phase, 4 grams of hexamethylenamine, 30 grams of polyformaldehyde, 2 grams of ethylenediamine, 50 grams of dimethylbenzene is added in reaction bulb
Heavy phase, hexamethylenamine, ethylenediamine, dimethylbenzene is heated to 50-60 DEG C, is dividedly in some parts polyformaldehyde, and 85-95 DEG C is warming up to after adding,
Insulation 1 hour, heat up dehydration to 105 DEG C or so, then vacuum dehydration gradually steps up vacuum to 0.095MPa, be dehydrated to
120-130 DEG C is kept for 30 minutes or so, adds 50 grams of dimethylbenzene so that the solid content of resin is stirred between 80%~90%
Uniformly, filtering and discharging.Viscosity 3350mPas contains 89.77% admittedly, yield 93.58%.
Embodiment 3
300 grams of heavy phase, 4 grams of hexamethylenamine, 45 grams of polyformaldehyde, 4 grams of ethylenediamine, 80 grams of dimethylbenzene is added in reaction bulb
Heavy phase, hexamethylenamine, ethylenediamine, dimethylbenzene is heated to 50-60 DEG C, is dividedly in some parts polyformaldehyde, and 85-95 DEG C is warming up to after adding,
Insulation 1 hour, heat up dehydration to 105 DEG C or so, then vacuum dehydration gradually steps up vacuum to 0.095MPa, be dehydrated to
120-130 DEG C is kept for 30 minutes or so, adds 50 grams of dimethylbenzene so that the solid content of resin is stirred between 80%~90%
Uniformly, filtering and discharging.Viscosity 3050mPas contains 89.567% admittedly, yield 95.58%.
Claims (3)
1. a kind of preparation method of phenol-formaldehyde resin modified, it is characterised in that：Comprise the steps：
1) heavy phase, polyformaldehyde, hexamethylenamine, ethylenediamine, dimethylbenzene are weighed according to material ratio, described heavy phase and polyformaldehyde rub
, than being 1: 1.2-4, the quality of described hexamethylenamine is the 1-4% of heavy phase quality for you, and the quality of described ethylenediamine is heavy phase
The 1-4% of quality, the quality of described dimethylbenzene is the 20-60% of heavy phase quality；
2) heavy phase, hexamethylenamine, ethylenediamine and 30%~70% dimethylbenzene are added in reaction vessel, 50-60 DEG C is heated to,
Divide 2~5 batches of addition polyformaldehyde, 85-95 DEG C is warming up to after adding, be incubated 0.5~2 hour, heat up and be dehydrated to 100~110 DEG C,
Vacuum is dehydrated to 0.05~0.1MPa, is then kept for 20~40 minutes under conditions of 120-130 DEG C, adds surplus
Dimethylbenzene, stir, filtering and discharging obtains phenol-formaldehyde resin modified.
2. the preparation method of phenol-formaldehyde resin modified according to claim 1, it is characterised in that：Described heavy phase be
1000Pa, the distillation substrate remained during cashew shell oil distillation extraction Cardanol under the conditions of 220~240 DEG C, molecular weight exists
Between 300-1000.
3. the preparation method of phenol-formaldehyde resin modified according to claim 2, it is characterised in that：Contain in described distillation substrate
There are cashew acid, Cardanol dimer, Cardanol trimer, Cardanol polymer or cashew acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611271486.8A CN106674456B (en) | 2016-12-30 | 2016-12-30 | Preparation method of modified phenolic resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611271486.8A CN106674456B (en) | 2016-12-30 | 2016-12-30 | Preparation method of modified phenolic resin |
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| Publication Number | Publication Date |
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| CN106674456A true CN106674456A (en) | 2017-05-17 |
| CN106674456B CN106674456B (en) | 2019-12-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611271486.8A Expired - Fee Related CN106674456B (en) | 2016-12-30 | 2016-12-30 | Preparation method of modified phenolic resin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803887A (en) * | 2005-12-31 | 2006-07-19 | 四川东材企业集团有限公司 | Benzoxazine resin containing aralkyl structure, its preparation method and use |
| CN103275285A (en) * | 2013-06-13 | 2013-09-04 | 湖南中野高科技特种材料有限公司 | Method for producing phenolic resin by partially using distilled carbolic oil instead of phenol |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
-
2016
- 2016-12-30 CN CN201611271486.8A patent/CN106674456B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803887A (en) * | 2005-12-31 | 2006-07-19 | 四川东材企业集团有限公司 | Benzoxazine resin containing aralkyl structure, its preparation method and use |
| CN103275285A (en) * | 2013-06-13 | 2013-09-04 | 湖南中野高科技特种材料有限公司 | Method for producing phenolic resin by partially using distilled carbolic oil instead of phenol |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
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| CN106674456B (en) | 2019-12-13 |
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| PB01 | Publication | ||
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| TA01 | Transfer of patent application right | ||
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Effective date of registration: 20191108 Address after: 239500, No. three, No. 17, Quanjiao Economic Development Zone, Chuzhou, Anhui Applicant after: ANHUI MEIDONG BIOLOGICAL MATERIAL Co.,Ltd. Address before: 201203, room 328, 302 Edison Road, Zhangjiang hi tech park, Shanghai, Pudong New Area Applicant before: SHANGHAI MEIDONG BIOLOGICAL MATERIAL CO.,LTD. |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
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Denomination of invention: Modified phenol formaldehyde resin preparation method Effective date of registration: 20200601 Granted publication date: 20191213 Pledgee: Quanjiao sub branch of Huishang Bank Co.,Ltd. Pledgor: ANHUI MEIDONG BIOLOGICAL MATERIAL Co.,Ltd. Registration number: Y2020980002657 |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191213 Termination date: 20211230 |