CN112063104A - Modified powder phenolic resin and preparation method and application thereof - Google Patents
Modified powder phenolic resin and preparation method and application thereof Download PDFInfo
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- CN112063104A CN112063104A CN202010987115.XA CN202010987115A CN112063104A CN 112063104 A CN112063104 A CN 112063104A CN 202010987115 A CN202010987115 A CN 202010987115A CN 112063104 A CN112063104 A CN 112063104A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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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
- C08G8/04—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
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention provides a modified powder phenolic resin and a preparation method and application thereof. The phenolic resin is obtained by blending and modifying a thermoplastic phenolic resin mixture, wherein the thermoplastic phenolic resin mixture comprises: 180-220 parts of thermoplastic phenolic resin, 15-30 parts of curing agent, 8-25 parts of calcium sulfate whisker and 6-30 parts of wollastonite powder. The preparation method comprises the following steps: preparing thermoplastic phenolic resin; and uniformly mixing the thermoplastic phenolic resin with a curing agent, calcium sulfate whiskers and wollastonite powder to obtain the phenolic resin. The modified powder phenolic resin is applied to friction materials. The heat fade critical temperature of the resulting friction material is increased by at least 6 ℃ and the wear resistance (250 ℃) is increased by at least 9.5% compared to the prior friction material.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to modified powder phenolic resin and a preparation method and application thereof.
Background
Phenolic resin, also called bakelite powder, is a multifunctional material compatible with a wide variety of organic and inorganic fillers. Phenolic resin is widely used in friction materials, mainly as a matrix (binder) of the friction material. The phenolic resin product for the friction material is thermoplastic phenolic resin formed by condensation polymerization of phenol and formaldehyde under the action of an acid catalyst, and has the characteristics of low free phenol, high thermal decomposition temperature, good fluidity, strong infiltration capacity on fibers and fillers and the like. In order to maintain the advantages of phenol resins for friction materials, higher demands are made on the production of phenol resins, and higher heat resistance and thermal stability are required than those of ordinary phenol resins. However, at present, the matrix phenolic resin of the domestic friction material is modified by boron, so that the heat resistance of the matrix phenolic resin is improved to a certain extent, but the matrix phenolic resin cannot fully meet the market demand.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a modified powder phenolic resin and a preparation method and application thereof. The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a modified powdered phenolic resin obtained by blending and modifying a thermoplastic phenolic resin mixture, wherein the thermoplastic phenolic resin mixture comprises: 180-220 parts of thermoplastic phenolic resin, 15-30 parts of curing agent, 8-25 parts of calcium sulfate whisker and 6-30 parts of wollastonite powder.
Preferably, the phenolic novolac resin mixture comprises: 180-220 parts of thermoplastic phenolic resin, 15-20 parts of curing agent, 15-20 parts of calcium sulfate whisker and 10-15 parts of wollastonite powder.
Further, the curing agent is urotropin.
Further, the particle size of the modified powder phenolic resin is not more than 5% and is more than 200 meshes.
In a second aspect, the invention provides a preparation method of a modified powder phenolic resin, which comprises the following steps:
s1, preparing thermoplastic phenolic resin;
s2, uniformly mixing the thermoplastic phenolic resin with the curing agent, the calcium sulfate whisker and the wollastonite powder to obtain the phenolic resin.
Further, the preparing the thermoplastic phenolic resin comprises:
(1) 200 parts of phenol, 100-160 parts of formaldehyde and 0.5-2.5 parts of weak acid catalyst are mixed;
(2) uniformly mixing phenol, formaldehyde and 1/2-3/5 weak acid catalyst, heating to boiling, and keeping the temperature for 15-30 min;
(3) adding the rest weak acid catalyst, and continuously preserving the heat for 1-2 hours;
(4) and removing water in the reaction liquid, stopping heating when the temperature of the dehydrated material reaches 190-195 ℃, and cooling to room temperature to obtain the catalyst.
Further, the uniformly mixing the thermoplastic phenolic resin with the curing agent, the calcium sulfate whisker and the wollastonite powder comprises the following steps: the preparation method comprises the steps of crushing the thermoplastic phenolic resin into blocks with the particle size of 10-20 mm, adding a curing agent, calcium sulfate whiskers and wollastonite powder, and crushing the blocks into powder with the particle size of more than 200 meshes being not more than 5% through high-speed airflow.
In a third aspect, the invention provides an application of the modified powder phenolic resin or the modified powder phenolic resin obtained by the preparation method in a friction material.
In a fourth aspect, the invention provides a friction material, which comprises the modified powdered phenolic resin or the modified powdered phenolic resin obtained by the preparation method.
Compared with the prior art, the invention has the following outstanding advantages and positive effects:
the invention prepares the powdery phenolic resin for the high-end friction material by a blending modification technology, and the powdery phenolic resin can replace the existing phenolic resin and be used in friction material products. A friction material having high wear resistance and heat fading resistance can be produced without changing the manufacturing process of the friction material, wherein the heat fading critical temperature of the obtained friction material is increased by at least 6 ℃ and the wear resistance (250 ℃) is increased by at least 9.5% compared with the existing friction material.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the modified powder phenolic resin of the present invention.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The embodiment provides a modified powder phenolic resin, which comprises the following components in parts by weight: 200 parts of thermoplastic phenolic resin, 15 parts of urotropine curing agent, 10 parts of calcium sulfate whisker and 12 parts of wollastonite powder. The preparation method of the modified powder phenolic resin comprises the following steps:
(1) 200 parts of phenol, 100 parts of formaldehyde and 2.5 parts of weak acid catalyst are mixed;
(2) uniformly mixing phenol, formaldehyde and 1.5 parts of weak acid catalyst, heating to boil, and preserving heat for 30 min;
(3) adding the rest weak acid catalyst, and continuously preserving the heat for 1.5 h;
(4) and (3) decompressing and dehydrating until the vacuum degree is 0.09MPa, stopping dehydrating when the temperature of the dehydrated material reaches 195 ℃, and cooling to room temperature to obtain the thermoplastic phenolic resin.
(5) The preparation method comprises the steps of crushing the thermoplastic phenolic resin into blocks with the particle size of 10-20 mm, adding the urotropine curing agent, the calcium sulfate whisker and the wollastonite powder, and crushing the materials into powder with the particle size of more than 200 meshes being not more than 5% through high-speed airflow to obtain the phenolic resin.
Example 2
The embodiment provides a modified powder phenolic resin, which comprises the following components in parts by weight: 180 parts of thermoplastic phenolic resin, 30 parts of urotropine curing agent, 25 parts of calcium sulfate whisker and 20 parts of wollastonite powder. The preparation method of the modified powder phenolic resin comprises the following steps:
(1) 200 parts of phenol, 120 parts of formaldehyde and 2.0 parts of weak acid catalyst are mixed;
(2) uniformly mixing phenol, formaldehyde and 1.2 parts of weak acid catalyst, heating to boil, and preserving heat for 30 min;
(3) adding the rest weak acid catalyst, and continuously preserving the heat for 1.5 h;
(4) and (3) decompressing and dehydrating until the vacuum degree is 0.09MPa, stopping dehydrating when the temperature of the dehydrated material reaches 190 ℃, and cooling to room temperature to obtain the thermoplastic phenolic resin.
(5) The preparation method comprises the steps of crushing the thermoplastic phenolic resin into blocks with the particle size of 10-20 mm, adding the urotropine curing agent, the calcium sulfate whisker and the wollastonite powder, and crushing the materials into powder with the particle size of more than 200 meshes being not more than 5% through high-speed airflow to obtain the phenolic resin.
Example 3
The embodiment provides a modified powder phenolic resin, which comprises the following components in parts by weight: 220 parts of thermoplastic phenolic resin, 20 parts of urotropine curing agent, 8 parts of calcium sulfate whisker and 6 parts of wollastonite. The preparation method of the modified powder phenolic resin comprises the following steps:
(1) 200 parts of phenol, 140 parts of formaldehyde and 1.5 parts of weak acid catalyst are mixed;
(2) uniformly mixing phenol, formaldehyde and 0.8 part of weak acid catalyst, heating to boil, and preserving heat for 20 min;
(3) adding the rest weak acid catalyst, and keeping the temperature for 1 h;
(4) and (3) decompressing and dehydrating until the vacuum degree is 0.09MPa, stopping dehydrating when the temperature of the dehydrated material reaches 195 ℃, and cooling to room temperature to obtain the thermoplastic phenolic resin.
(5) The preparation method comprises the steps of crushing the thermoplastic phenolic resin into blocks with the particle size of 10-20 mm, adding the urotropine curing agent, the calcium sulfate whisker and the wollastonite powder, and crushing the materials into powder with the particle size of more than 200 meshes being not more than 5% through high-speed airflow to obtain the phenolic resin.
Example 4
The embodiment provides a modified powder phenolic resin, which comprises the following components in parts by weight: 200 parts of thermoplastic phenolic resin, 15 parts of urotropine curing agent, 20 parts of calcium sulfate whisker and 15 parts of wollastonite powder. The preparation method of the modified powder phenolic resin comprises the following steps:
(1) 200 parts of phenol, 160 parts of formaldehyde and 2.0 parts of weak acid catalyst are mixed;
(2) uniformly mixing phenol, formaldehyde and 1.0 part of weak acid catalyst, heating to boil, and preserving heat for 30 min;
(3) adding the rest weak acid catalyst, and continuously preserving the heat for 2 hours;
(4) and (3) decompressing and dehydrating until the vacuum degree is 0.09MPa, stopping dehydrating when the temperature of the dehydrated material reaches 195 ℃, and cooling to room temperature to obtain the thermoplastic phenolic resin.
(5) The preparation method comprises the steps of crushing the thermoplastic phenolic resin into blocks with the particle size of 10-20 mm, adding the urotropine curing agent, the calcium sulfate whisker and the wollastonite powder, and crushing the materials into powder with the particle size of more than 200 meshes being not more than 5% through high-speed airflow to obtain the phenolic resin.
Comparative example 1
This comparative example provides a powdered phenolic resin prepared as in example 4, but without the addition of wollastonite powder.
Comparative example 2
This comparative example provides a powdered phenolic resin prepared as in example 4, but without the addition of calcium sulfate whiskers.
The phenolic resins of examples 1 to 4 and comparative examples 1 to 2 were prepared into drum brake pads, the process is prior art and will not be described in detail herein, and the performance of these brake pads was tested and the results are shown in table 1:
the data in table 1 show that phenolic resin with excellent performance can be obtained by compounding wollastonite powder and calcium sulfate whiskers as a blending material, so that a friction material with excellent performance is obtained, the heat fading critical temperature of the friction material is improved by at least 6 ℃ compared with that of the conventional friction material, and the abrasion resistance (250 ℃) of the friction material is improved by at least 9.5% compared with that of the conventional friction material. In addition, as can be seen from the disclosed heat fading critical temperature and abrasion resistance of the drum brake pad prepared by the comparative example, the performance of the phenolic resin can be improved by adding the wollastonite powder and the calcium sulfate whiskers to the thermoplastic phenolic resin.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A modified powder phenolic resin is characterized in that: the phenolic resin is obtained by blending and modifying a thermoplastic phenolic resin mixture, wherein the thermoplastic phenolic resin mixture comprises: 180-220 parts of thermoplastic phenolic resin, 15-30 parts of curing agent, 8-25 parts of calcium sulfate whisker and 6-30 parts of wollastonite powder.
2. The modified powdery phenolic resin as claimed in claim 1, wherein: the thermoplastic phenolic resin mixture comprises: 180-220 parts of thermoplastic phenolic resin, 15-20 parts of curing agent, 15-20 parts of calcium sulfate whisker and 10-15 parts of wollastonite powder.
3. The modified powdery phenol resin according to claim 1 or 2, characterized in that: the curing agent is urotropin.
4. The modified powdery phenolic resin as claimed in claim 1, wherein: the particle of 200 meshes above in the modified powder phenolic resin is not higher than 5%.
5. The method for preparing a modified powdery phenol resin according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
s1, preparing thermoplastic phenolic resin;
s2, uniformly mixing the thermoplastic phenolic resin with the curing agent, the calcium sulfate whisker and the wollastonite powder to obtain the phenolic resin.
6. The method for preparing modified powdery phenolic resin according to claim 5, characterized in that: the preparation of the thermoplastic phenolic resin comprises the following steps:
(1) 200 parts of phenol, 100-160 parts of formaldehyde and 0.5-2.5 parts of weak acid catalyst are mixed;
(2) uniformly mixing phenol, formaldehyde and 1/2-3/5 weak acid catalyst, heating to boiling, and keeping the temperature for 15-30 min;
(3) adding the rest weak acid catalyst, and continuously preserving the heat for 1-2 hours;
(4) and removing water in the reaction liquid, stopping heating when the temperature of the dehydrated material reaches 190-195 ℃, and cooling to room temperature to obtain the catalyst.
7. The method for preparing modified powdery phenolic resin according to claim 5, characterized in that: the step of uniformly mixing the thermoplastic phenolic resin with the curing agent, the calcium sulfate whisker and the wollastonite powder comprises the following steps: the preparation method comprises the steps of crushing the thermoplastic phenolic resin into blocks with the particle size of 10-20 mm, adding a curing agent, calcium sulfate whiskers and wollastonite powder, and crushing the blocks into powder with the particle size of more than 200 meshes being not more than 5% through high-speed airflow.
8. Use of the modified phenolic powder resin according to any one of claims 1 to 4 or the modified phenolic powder resin obtained by the preparation method according to any one of claims 5 to 7 in a friction material.
9. A friction material characterized by: the modified phenolic powder resin comprises the modified phenolic powder resin as claimed in any one of claims 1 to 4 or the modified phenolic powder resin obtained by the preparation method as claimed in any one of claims 5 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010987115.XA CN112063104A (en) | 2020-09-18 | 2020-09-18 | Modified powder phenolic resin and preparation method and application thereof |
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| CN202010987115.XA CN112063104A (en) | 2020-09-18 | 2020-09-18 | Modified powder phenolic resin and preparation method and application thereof |
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| CN112063104A true CN112063104A (en) | 2020-12-11 |
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| CN202010987115.XA Pending CN112063104A (en) | 2020-09-18 | 2020-09-18 | Modified powder phenolic resin and preparation method and application thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751435A (en) * | 2017-02-17 | 2017-05-31 | 王利英 | A kind of elevator flame-retardant and anti-static friction lining and preparation method thereof |
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- 2020-09-18 CN CN202010987115.XA patent/CN112063104A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751435A (en) * | 2017-02-17 | 2017-05-31 | 王利英 | A kind of elevator flame-retardant and anti-static friction lining and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邹宽生 等: "《胶粘剂生产工艺》", 31 July 2002, 高等教育出版社 * |
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Application publication date: 20201211 |
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