CN107189305A - A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material - Google Patents
A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material Download PDFInfo
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- CN107189305A CN107189305A CN201710506228.1A CN201710506228A CN107189305A CN 107189305 A CN107189305 A CN 107189305A CN 201710506228 A CN201710506228 A CN 201710506228A CN 107189305 A CN107189305 A CN 107189305A
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- isocyanate
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- pulp
- latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
Strengthen the preparation method of Latex Gasket Sheet Crosslinked material the invention discloses a kind of isocyanate-crosslinked acrylic fibers pulp, there is microcosmic phase separation using polyurethane and polyacrylonitrile in the present invention, make pulp more easily fibrillable, thus gained pulp is smaller, evenly, specific surface area is improved, blocked isocyanate is used as crosslinking agent in addition, when high temperature vulcanized, NCO group activity recovery can be made, with the hydroxyl in rubber latex, chemical crosslinking occurs between carboxyl and the hydroxyl on pulp fibers surface and forms three-dimension interaction network, firm covalent bond is formd to be glued, so that the tensile strength of gasket seal material is significantly improved with Shao Er hardness, the mechanical property of material significantly improves.
Description
Technical field
The present invention relates to a kind of preparation method of gasket seal, and in particular to a kind of isocyanate-crosslinked acrylic fibers pulp enhancing
The preparation method of Latex Gasket Sheet Crosslinked material.
Background technology
The non-asbestos of fibre reinforced elastomer encapsulant, is the trend of current environmental protection development.The U.S., Japan and Australia are big
Many companies of Leah replaced asbestos early in 1984 with aromatic polyamide heatproof organic fiber or carbon fiber, using compression
Asbestos (CA) method produces non-asbestos seal gasket material.Because the industries such as food, medicine, light industry, ship, car increase to non-asbestos
The wilderness demand of strong rubber sheet gasket, over more than 10 years, China's relevant industries have carried out Co-operation research and have achieved greater advance.With virtue
Sulfone synthetic fibre, aramid fiber, glass or carbon fiber replace asbestos, middle high-pressure non-asbestos fibre elastomeric material are developed, then in non-stone
Further optimization is made in terms of the moulding process of the selection of cotton fiber, rubber adhesive and sheet material, portioned product has realized work
Industry.
But the tensile strength of prepared non-asbestos enhancing elastomeric material and corresponding asbestos friction material relaxes with creep resistant at present
The gap of ability is larger, and it is main reason is that non-asbestos synthetic fibers surface relative smooth, rubber adhesive, inorganic filler are difficult
In infiltrating, spreading and infiltrating into fiber micropore, cause its mechanical adhering force not enough.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of isocyanate-crosslinked acrylic fibers pulp enhancing Latex Gasket Sheet Crosslinked
The preparation method of material, the isocyanate groups of high activity form firm covalent bond glue in fiber, rubber latex and filler
Connect, compensate for the deficiency of mechanical adhering force therebetween and Hydrogen bonding forces, making the mechanical property of encapsulant improves notable.
The present invention is achieved by the following technical solutions：
A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material, and its preparation technology includes following
Step：
（1）The preparation of hydroxyl-terminated polyurethane performed polymer：
6-14 parts by weight PPG is vacuumized into removing moisture to moisture content below 0.5%, so at 108-115 DEG C first
It is added drop-wise under nitrogen atmosphere afterwards in 3-9 parts of organic polyisocyanate compounds, reacted 1-3 hours at 50-85 DEG C, plus
Enter and reacted again after 0.5-3 parts of sodium hydrogensulfites 10-60 minutes, obtain hydroxyl-terminated polyurethane performed polymer；
（2）The preparation of mixed serum：
65-90 parts of polyacrylonitrile are placed in convection oven, it is standby in being dried 6-8 hours at 78-83 DEG C；By 120-180 parts of N,
N- dimethyl acetamides pour into three-necked bottle, and turn on agitator stirring adds 2-6 parts of lithium chlorides after after its dissolving completely, added dry
Dry good polyacrylonitrile, is put into water-bath and is heated to 78-83 DEG C of stirring fully dissolving, be cooled to after room temperature and add above-mentioned terminal hydroxy group
Base polyurethane prepolymer for use as, is mixed evenly；
（3）Under high speed shear effect, in the solidification liquid that polyacrylonitrile/polyurethane mixed serum injection is prepared, 10- is sheared
After 20 minutes, suction filtration is washed with deionized 2-4 times, centrifugal drying, obtains that pulp is blended；
（4）Above-mentioned blending pulp is added in deionized water, high speed shear is uniformly dispersed, add 2-4 parts of blocked isocyanates
Crosslinking agent, 10-23 part rubber latex, 0.02-0.1 parts of defoamers and 0.04-0.2 parts of sulphur are mixed evenly, and are formed homogeneous
Suspension, after take shaping through copying；
（5）Dry, vulcanize：
After product drying after above-mentioned shaping, under the conditions of sulfide stress 4.5-6.7MPa, 125-150 DEG C of curing temperature, vulcanization
10-20 minutes, produce.
Wherein, the organic polyisocyanate compound is that 2,4- toluene di-isocyanate(TDI)s, diphenyl methane -4,4- bis- are different
Any one in cyanate, hexamethylene diisocyanate or 4,4'- dicyclohexyl methyl hydride diisocyanates.
Wherein, described solidification liquid refers to the mixed solution of DMA and water, and both volume ratios are 1-
3:1。
Wherein, described rubber latex refers to that carboxylic styrene-butadiene rubber emulsion is mixed with XNBR emulsion with any ratio
Form.
Described closed isocyanate crosslinker refers to utilize sodium disulfide, sodium hydrogensulfite, sodium pyrosulfate and over cure
The aqueous solution of sour sodium reacts the water dispersible sodium disulfide blocked isocyanate prepared with isocyanates.
Compared with prior art, the present invention has advantages below：
（1）The hydroxyl-terminated polyurethane used in the present invention in DMA, makes with polyacrylonitrile energy co-dissolve
Polyurethane is dispersed in polyacrylonitrile slurries, in precipitating forming process, and dispersed phase polyurethane is similarly in the solidifying of flowing
Gu sheared in bath and stretch and deform, due to two it is alternate there is microcosmic phase separation, nascent pulp is there is substantial amounts of distribution
Uniform weak spot, in the presence of shearing force, pulp is easy to, in the fracture of these weak spots or longitudinal splitting, realize fibrillation,
Thus gained pulp is smaller, evenly, and specific surface area is improved, while introducing more-OH poles on pulp surface
Property group, improve more avtive spots.
（2）The present invention use blocked isocyanate as crosslinking agent, when high temperature vulcanized, can make-NCO group recovers work
Property, generation chemical crosslinking forms three-dimension interaction between the hydroxyl of the hydroxyl in rubber latex, carboxyl and pulp fibers surface
Network, forms firm covalent bond and is glued so that the tensile strength of gasket seal material is significantly improved with Shao Er hardness, material
Mechanical property significantly improve.
Embodiment
A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material, and its preparation technology includes
Following steps：
（1）The preparation of hydroxyl-terminated polyurethane performed polymer：
14 parts by weight PPGs are vacuumized into removing moisture to moisture content below 0.5%, then by it at 110 DEG C first
It is added drop-wise in 9 parts of 2,4- toluene di-isocyanate(TDI)s, is reacted 2 hours at 65 DEG C under nitrogen atmosphere, adds 0.8 part of bisulfite
Reacted again after sodium 40 minutes, obtain hydroxyl-terminated polyurethane performed polymer；
（2）The preparation of mixed serum：
80 parts of polyacrylonitrile are placed in convection oven, it is standby in being dried 8 hours at 80 DEG C；By 180 parts of N, N- dimethylacetamides
Amine pours into three-necked bottle, and turn on agitator stirring adds 6 parts of lithium chlorides after after its dissolving completely, adds dried polyacrylonitrile,
It is put into water-bath and is heated to 80 DEG C of stirrings fully dissolving, is cooled to after room temperature and adds above-mentioned hydroxyl-terminated polyurethane performed polymer, mix
Stir；
（3）Under high speed shear effect, in the solidification liquid that polyacrylonitrile/polyurethane mixed serum injection is prepared, shearing 15
After minute, suction filtration is washed with deionized 4 times, centrifugal drying, obtains that pulp is blended；
（4）Above-mentioned blending pulp is added in deionized water, high speed shear is uniformly dispersed, add 4 parts of blocked isocyanates and hand over
Connection agent, 20 parts of XNBR emulsions, 0.05 part of defoamer and 0.08 part of sulphur are mixed evenly, and form homogeneous suspension
Liquid, after take shaping through copying；
（5）Dry, vulcanize：
After product drying after above-mentioned shaping, under the conditions of sulfide stress 4.5MPa, 150 DEG C of curing temperature, vulcanization 20 minutes, i.e.,
.
Wherein, described solidification liquid refers to the mixed solution of DMA and water, and both volume ratios are 3:
1。
Described closed isocyanate crosslinker refers to utilize sodium disulfide, sodium hydrogensulfite, sodium pyrosulfate and over cure
The aqueous solution of sour sodium reacts the water dispersible sodium disulfide blocked isocyanate prepared with isocyanates.
Claims (5)
1. a kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material, it is characterised in that it is made
Standby technique comprises the following steps：
（1）The preparation of hydroxyl-terminated polyurethane performed polymer：
6-14 parts by weight PPG is vacuumized into removing moisture to moisture content below 0.5%, so at 108-115 DEG C first
It is added drop-wise under nitrogen atmosphere afterwards in 3-9 parts of organic polyisocyanate compounds, reacted 1-3 hours at 50-85 DEG C, plus
Enter and reacted again after 0.5-3 parts of sodium hydrogensulfites 10-60 minutes, obtain hydroxyl-terminated polyurethane performed polymer；
（2）The preparation of mixed serum：
65-90 parts of polyacrylonitrile are placed in convection oven, it is standby in being dried 6-8 hours at 78-83 DEG C；By 120-180 parts of N,
N- dimethyl acetamides pour into three-necked bottle, and turn on agitator stirring adds 2-6 parts of lithium chlorides after after its dissolving completely, added dry
Dry good polyacrylonitrile, is put into water-bath and is heated to 78-83 DEG C of stirring fully dissolving, be cooled to after room temperature and add above-mentioned terminal hydroxy group
Base polyurethane prepolymer for use as, is mixed evenly；
（3）Under high speed shear effect, in the solidification liquid that polyacrylonitrile/polyurethane mixed serum injection is prepared, 10- is sheared
After 20 minutes, suction filtration is washed with deionized 2-4 times, centrifugal drying, obtains that pulp is blended；
（4）Above-mentioned blending pulp is added in deionized water, high speed shear is uniformly dispersed, add 2-4 parts of blocked isocyanates
Crosslinking agent, 10-23 part rubber latex, 0.02-0.1 parts of defoamers and 0.04-0.2 parts of sulphur are mixed evenly, and are formed homogeneous
Suspension, after take shaping through copying；
（5）Dry, vulcanize：
After product drying after above-mentioned shaping, under the conditions of sulfide stress 4.5-6.7MPa, 125-150 DEG C of curing temperature, vulcanization
10-20 minutes, produce.
2. a kind of isocyanate-crosslinked acrylic fibers pulp according to claims 1 strengthens the preparation of Latex Gasket Sheet Crosslinked material
Method, it is characterised in that the organic polyisocyanate compound is 2,4- toluene di-isocyanate(TDI)s, diphenyl methane -4,4-
Any one in diisocyanate, hexamethylene diisocyanate or 4,4'- dicyclohexyl methyl hydride diisocyanates.
3. a kind of isocyanate-crosslinked acrylic fibers pulp according to claims 1 strengthens the preparation of Latex Gasket Sheet Crosslinked material
Method, it is characterised in that described solidification liquid refers to the mixed solution of DMA and water, both volume ratios are
1-3:1。
4. a kind of isocyanate-crosslinked acrylic fibers pulp according to claims 1 strengthens the preparation of Latex Gasket Sheet Crosslinked material
Method, it is characterised in that described rubber latex refers to carboxylic styrene-butadiene rubber emulsion with XNBR emulsion arbitrarily to compare
Mix.
5. a kind of coating processes of basalt fibre size according to claims 1, it is characterised in that described envelope
Closed form isocyanate crosslinking refer to using sodium disulfide, sodium hydrogensulfite, the aqueous solution of sodium pyrosulfate and sodium peroxydisulfate with it is different
Water dispersible sodium disulfide blocked isocyanate prepared by polyisocyanate reactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710506228.1A CN107189305A (en) | 2017-06-28 | 2017-06-28 | A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710506228.1A CN107189305A (en) | 2017-06-28 | 2017-06-28 | A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material |
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| Publication Number | Publication Date |
|---|---|
| CN107189305A true CN107189305A (en) | 2017-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710506228.1A Pending CN107189305A (en) | 2017-06-28 | 2017-06-28 | A kind of isocyanate-crosslinked acrylic fibers pulp strengthens the preparation method of Latex Gasket Sheet Crosslinked material |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283013A (en) * | 2005-08-17 | 2008-10-08 | 圣戈班柴恩纽克斯特性塑料公司 | Hydrolysis resistant cellular material, the composition and method for the production thereof |
-
2017
- 2017-06-28 CN CN201710506228.1A patent/CN107189305A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283013A (en) * | 2005-08-17 | 2008-10-08 | 圣戈班柴恩纽克斯特性塑料公司 | Hydrolysis resistant cellular material, the composition and method for the production thereof |
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|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170922 |
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| RJ01 | Rejection of invention patent application after publication |