CN109251289A - A kind of preparation method of the phenolic resin with heat resistance and toughness - Google Patents
A kind of preparation method of the phenolic resin with heat resistance and toughness Download PDFInfo
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- CN109251289A CN109251289A CN201810917200.1A CN201810917200A CN109251289A CN 109251289 A CN109251289 A CN 109251289A CN 201810917200 A CN201810917200 A CN 201810917200A CN 109251289 A CN109251289 A CN 109251289A
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- phenolic resin
- heat resistance
- acid
- toughness
- 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
Abstract
A kind of preparation method of the phenolic resin with heat resistance and toughness, it is characterized by: under conditions of acidic catalyst or basic catalyst, phenolic compound and boride is set to generate aryl-boric acid ester, polyamide elastomer is dissolved in aryl-boric acid ester later, aldehyde compound is added, and the reaction was continued, to obtain thermoplastic phenolic resin powder or thermosetting phenolic resin liquid.Resin prepared by the present invention has good heat resistance, high fixing carbon with respect to phenolic resin, while having good toughness again, improves the big disadvantage of boron bakelite resin brittleness, is a kind of High Performance Phenolic Resins for having both heat resistance and toughness.
Description
Technical field
The invention belongs to macromolecule material preparation areas, and in particular to a kind of phenolic aldehyde tree for having both excellent heat resistance and toughness
The preparation method of rouge.
Background technique
With the continuous development of human society, requirement of the people to properties of product and quality is also being continuously improved, therefore more
It is applied in modern industry come more high rigidity, high-strength material.And these materials have excellent properties while, also go out
A series of problems, such as difficulty of processing is big, grinding area temperature is high, grinding tool loss is serious is showed.Resinoid bonded grinding tool has
Intensity is big, good toughness, self-sharpening are good, the advantages that being not easy to plug；But its heat resistance is poor, when grinding area temperature increases, tree
Rouge bonding agent can occur softening, decompose phenomena such as, decline to a great extent so as to cause holding power of the bonding agent to abrasive material, abrasive material not by
Just occurrence of large-area falls off in the case where abrasion, has seriously affected precision and efficiency when work pieces process, and grinding tool loss is serious, increases
Processing cost is added.
Boron bakelite resin, which refers to, uses boride as modifying agent, is changed in a manner of being blended or being copolymerized to phenolic resin
Property a resinoid, it is low in cost and have fabulous heat resistance and carbon yield.But it is often condensed between boride, from
And the modified phenolic resin degree of cross linking is increased, cause resin the problem that heat resistance is splendid but toughness is insufficient occur.Cui Jie
Etc. the heat resistance and mechanical property for having studied acrylonitrile butadiene rubber modified boron bakelite resin, discovery is acrylonitrile butadiene rubber modified so that resin is rushed
It hits toughness and improves nearly 1 times, but 400 DEG C or more of heat resistance decline.Guo Anru etc. has synthesized organosilicon using phenyl-borate method and has changed
Property boron bakelite resin, impact strength improves a lot, but due to the siloxanes segment of introducing easily occur at high temperature thermal decomposition and
Thermal oxide, therefore the heat resistance of resin and carbon yield can be greatly reduced at high temperature.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of phenolic resin binder for having both heat resistance and toughness, make
The resin is obtained while keeping the excellent self-sharpening of ordinary resin bonding agent and grinding performance, with excellent heat resistance and preferably
Toughness, to meet the process requirements of certain difficult-to-machine materials.
The purpose of the present invention can be realized by following technique measures:
The preparation method of phenolic resin with heat resistance and toughness of the invention in acid condition, phenolic compound and boron
Compound dehydrating condensation generates aryl-boric acid ester and its derivative, and polyamide elastomer is added and is allowed to reaction dissolution, then with aldehydes
It closes object reaction and generates thermoplastic phenolic resin.
The phenolic resin is made of the raw material of following mass parts: 100 parts of phenolic compound, 20 ~ 30 parts of aldehyde compound,
20 ~ 60 parts of boride, 1% ~ 5% acidic catalyst of 1 ~ 10 part of polyamide elastomer and above-mentioned raw materials gross mass；Preparation side
Method is as follows: taking phenolic compound, boride and acidic catalyst to be added in reaction unit by mass parts, slow gradient increased temperature
Reaction is to 190 ~ 210 DEG C, and the water that vacuum distillation is generated except dereaction in the process, obtains aryl-boric acid ester and its derivative,
So that reaction system is cooled to 85 ~ 95 DEG C or so later, adds polyamide elastomer and aldehyde compound is allowed to dissolve and stir
Uniformly, being heated to boiling, the reaction was continued to reaction end, and quickly discharging after vacuum dehydration generates thermoplastic phenolic resin；
Heretofore described phenolic compound be derived from phenol, bisphenol-A, Bisphenol F, catechol, resorcinol, to phenyl methylcarbamate, 1,
Several mixture of one or both of 4- benzenediol or 1,3,5- benzenetriol or more.
Heretofore described aldehyde compound be derived from one of formalin, paraformaldehyde, metaformaldehyde or furfural or
Two kinds or more several mixtures.
Heretofore described acidic catalyst is derived from sulfuric acid, oxalic acid, hydrochloric acid, acetic acid, phosphoric acid, citric acid or p-methyl benzenesulfonic acid
One or more of mixture.
Heretofore described boride be one or both of boric acid, borate, borax, boron carbide or halogenated boron and with
Upper several mixture.
Heretofore described polyamide elastomer refers to the polyamide of binary acid blocked and polyetherdiol or polyester-diol
Reaction be formed by the mixture of copolymer or several copolymers, reaction process and design feature approximately as:
Binary acid blocks the Amino End Group of polyamide, forms the intermediate that end group is carboxyl；If (binary acid is ethanedioic acid, R1
It is not present；
Intermediate continuation is reacted with polyester-diol or polyetherdiol, forms block copolymer, and the block copolymer can basis
It is hydroxy or carboxy that reactant ratio, which freely regulates and controls end group,；
The present invention has the following beneficial effects: compared with existing other methods
(1) phenolic resin is made has good heat resistance and high fixing carbon.
(2) in the case where guaranteeing that heat resistance does not reduce, the disadvantage of boron bakelite resin toughness deficiency is effectively improved, is promoted
Bending strength and impact strength.
Detailed description of the invention
Fig. 1 is thermoplastic phenolic resin structural schematic diagram of the invention.
R is polyamide elastomer in figure.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
The present invention is used as modifying agent using toughness and the preferable polyamide elastomer of heat resistance (TPAE), is introduced into boron phenolic
In resin, improve toughness in the case where not influencing boron bakelite resin itself excellent heat resistance, thus be made one kind have both it is excellent
The High Performance Phenolic Resins of heat resistance and excellent toughness.
Wherein polyamide elastomer (TPAE) is aliphatic polyester, polyethers or polycarbonate conduct using polyamide as hard section
The block polymer of soft segment, wherein the polyamide of composition TPAE hard section includes nylon66 fiber, nylon 610, nylon 612, nylon
11, the common nylon series such as nylon 12, soft segment includes polypropylene glycol (PPG), polytetrahydrofuran (PTMG) and polyethylene glycol
(PEG) the polyether polyesters quasi polymer such as.The general structure formula of typical nylon66 fiber type TPAE:
[PE-C(CH2)4CO[NH(CH2)6NHCO(CH2)4COO]n-PE]n
PE is the polyethers or polyester polyol as soft segment in above formula, and end group is hydroxyl and carboxyl.
The comprehensive performance of TPAE is that tensile strength and impact strength at low temperature are high, and flexibility is good, and elastic recovery rate is high, is had good
Good wearability and flexibility, the anti-fatigue performance of height, coefficient of friction is small, good thermal stability, and maximum operation (service) temperature is reachable
175 DEG C, and can be used for a long time at 150 DEG C.
High temperature generates differential responses degree under the action of catalyst for boride such as boric acid or diboron trioxide and phenol first
Boric acid phenolic ester mixture.
Then under the effect of the catalyst, the contraposition of the phenol in one side boric acid phenolic ester mixture or ortho position and formaldehyde are anti-
Boron bakelite resin should be generated,
Unreacted boron hydroxyl can be sent out with the hydroxy or carboxy in polyamide elastomer in another aspect boric acid phenolic ester mixture
Raw condensation reaction, to generate ehter bond or ester bond.Finally formed modified resin structure is as shown in Figure 1, wherein boron oxygen carbon key
High bond energy assigns resin excellent heat resistance, and polyamide elastomer assigns resin excellent toughness, to reach heat resistance and tough
Phenol-formaldehyde resin modified both with property.
Embodiment 1:
By 94.11g phenol, 24.8g boric acid, 2.4g oxalic acid is added with agitating paddle, thermometer and condenser pipe, three mouthfuls of water segregator
In flask, being heated to 90 DEG C stablizes reaction system, and slow gradient increased temperature is reacted to 200 DEG C in 5h later, until glass point
No liquid occurs in hydrophone, the water that vacuum distillation is generated except dereaction.So that reaction system is cooled to 90 DEG C or so later, 5g is added
Polyamide elastomer (1000 copolymer of PA1212-b-PTMG1000 polyamide 1212- polytetrahydrofuran ether, self-control) is stirred to molten
Solution, adds 37% formalin of 70.54g, and at 100 DEG C or so, the reaction was continued to terminal, quickly goes out after high-temperature vacuum dehydration
Material generates phenol-formaldehyde resin modified.421 DEG C of initial pyrolyzation temperature are measured using resistance to STA409C synchronous solving of speeding, according to
GB/T9341-2000 and GB/T 1043.1-2008 standard testing bending strength 42.5MPa, impact strength 3.23kJ/m2。
Embodiment 2:
By 94.11g phenol, 20.6g boric acid, 2.4g hydrochloric acid and appropriate water entrainer are added with agitating paddle, thermometer and glass point
In the three-necked flask of hydrophone, being heated to 90 DEG C stablizes reaction system, and slow gradient increased temperature is reacted to 190 DEG C in 5h later,
Until no liquid occurs in glass trap, vacuum distillation removes the water that dereaction generates.Reaction system is set to be cooled to 90 DEG C later
Left and right, 3g polyamide elastomer (PA66-b-PEG2000 polyamide 66-polyethylene glycol 2000 copolymer, self-control) is added, and stirring is extremely
Dissolution, adds the paraformaldehyde of 26g, and at 110 DEG C or so, the reaction was continued to terminal, quickly discharging after high-temperature vacuum dehydration, raw
At phenol-formaldehyde resin modified.416 DEG C of initial pyrolyzation temperature are measured using resistance to STA409C synchronous solving of speeding, according to GB/
T9341-2000 and GB/T 1043.1-2008 standard testing bending strength 44.8MPa, impact strength 3.61kJ/m2。
Claims (6)
1. a kind of preparation method of the phenolic resin with heat resistance and toughness, it is characterised in that: in acid condition, phenols
Compound and boride dehydrating condensation generate aryl-boric acid ester and its derivative, and polyamide elastomer is added and is allowed to reaction dissolution,
It is reacted again with aldehyde compound and generates thermoplastic phenolic resin；
The phenolic resin is made of the raw material of following mass parts: 100 parts of phenolic compound, 20 ~ 30 parts of aldehyde compound, and boronation
20 ~ 60 parts of object, 1% ~ 5% acidic catalyst of 1 ~ 10 part of polyamide elastomer and above-mentioned raw materials gross mass；Preparation method is such as
Under: take phenolic compound, boride and acidic catalyst to be added in reaction unit by mass parts, slow gradient increased temperature reaction
To 190 ~ 210 DEG C, and the water that vacuum distillation is generated except dereaction in the process, aryl-boric acid ester and its derivative are obtained, later
So that reaction system is cooled to 85 ~ 95 DEG C or so, add polyamide elastomer and aldehyde compound is allowed to dissolve and stir evenly,
Being heated to boiling, the reaction was continued to reaction end, and quickly discharging after vacuum dehydration generates thermoplastic phenolic resin.
2. the preparation method of the phenolic resin according to claim 1 with heat resistance and toughness, it is characterised in that: institute
State phenolic compound be derived from phenol, bisphenol-A, Bisphenol F, catechol, resorcinol, to phenyl methylcarbamate, 1,4- benzenediol or 1,3,
Several mixture of one or both of 5- benzenetriol or more.
3. the preparation method of the phenolic resin according to claim 1 with heat resistance and toughness, it is characterised in that: institute
It states aldehyde compound and is derived from several mixed of one or both of formalin, paraformaldehyde, metaformaldehyde or furfural or more
Close object.
4. the preparation method of the phenolic resin according to claim 1 with heat resistance and toughness, it is characterised in that: institute
It states acidic catalyst and is derived from the mixed of one or more of sulfuric acid, oxalic acid, hydrochloric acid, acetic acid, phosphoric acid, citric acid or p-methyl benzenesulfonic acid
Close object.
5. the preparation method of the phenolic resin according to claim 1 with heat resistance and toughness, it is characterised in that: institute
It states polyamide elastomer and refers to react with the polyamide of binary acid blocked with polyetherdiol or polyester-diol and be formed by copolymer
Or the mixture of several copolymers, reaction process and design feature approximately as:
Binary acid blocks the Amino End Group of polyamide, forms the intermediate that end group is carboxyl；Wherein, if binary acid is ethanedioic acid,
Then R1It is not present；
Intermediate continuation is reacted with polyester-diol or polyetherdiol, forms block copolymer, and the block copolymer can basis
It is hydroxy or carboxy that reactant ratio, which freely regulates and controls end group,；
。
6. the preparation method of the phenolic resin according to claim 1 with heat resistance and toughness, it is characterised in that: institute
Stating boride is one or both of boric acid, borate, borax, boron carbide or halogenated boron or more several mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810917200.1A CN109251289B (en) | 2018-08-13 | 2018-08-13 | Preparation method of phenolic resin with heat resistance and toughness |
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| CN201810917200.1A CN109251289B (en) | 2018-08-13 | 2018-08-13 | Preparation method of phenolic resin with heat resistance and toughness |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484176A (en) * | 2019-09-30 | 2019-11-22 | 河南工业大学 | A kind of preparation method of modified silicon phenolic resin adhesive |
| CN111072884A (en) * | 2019-12-04 | 2020-04-28 | 沈阳化工大学 | Preparation method of palmitoyl hexadecane diol modified phenolic resin |
| CN111499818A (en) * | 2020-06-09 | 2020-08-07 | 河南省科学院高新技术研究中心 | Method for preparing thermoplastic boron phenolic resin by solid-phase synthesis method |
| CN115319648A (en) * | 2022-03-02 | 2022-11-11 | 淄博理研泰山涂附磨具有限公司 | Long-life abrasive cloth and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484176A (en) * | 2019-09-30 | 2019-11-22 | 河南工业大学 | A kind of preparation method of modified silicon phenolic resin adhesive |
| CN110484176B (en) * | 2019-09-30 | 2021-09-03 | 河南工业大学 | Preparation method of modified silicon phenolic resin adhesive |
| CN111072884A (en) * | 2019-12-04 | 2020-04-28 | 沈阳化工大学 | Preparation method of palmitoyl hexadecane diol modified phenolic resin |
| CN111072884B (en) * | 2019-12-04 | 2023-03-28 | 沈阳化工大学 | Preparation method of palmitoyl hexadecanediol modified phenolic resin |
| CN111499818A (en) * | 2020-06-09 | 2020-08-07 | 河南省科学院高新技术研究中心 | Method for preparing thermoplastic boron phenolic resin by solid-phase synthesis method |
| CN111499818B (en) * | 2020-06-09 | 2023-01-24 | 河南省科学院高新技术研究中心 | Method for preparing thermoplastic boron phenolic resin by solid-phase synthesis method |
| CN115319648A (en) * | 2022-03-02 | 2022-11-11 | 淄博理研泰山涂附磨具有限公司 | Long-life abrasive cloth and preparation method thereof |
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