CN113957717B - Ultrahigh molecular weight polyethylene fiber reinforced material and preparation method thereof - Google Patents
Ultrahigh molecular weight polyethylene fiber reinforced material and preparation method thereof Download PDFInfo
- Publication number
- CN113957717B CN113957717B CN202111346951.0A CN202111346951A CN113957717B CN 113957717 B CN113957717 B CN 113957717B CN 202111346951 A CN202111346951 A CN 202111346951A CN 113957717 B CN113957717 B CN 113957717B
- Authority
- CN
- China
- Prior art keywords
- bath
- dipping
- stirring
- molecular weight
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Abstract
The invention provides an ultra-high molecular weight polyethylene reinforced material and a preparation method thereof, comprising a three-bath dipping method, wherein a first bath dipping liquid, a second bath dipping liquid and a third bath dipping liquid are used for respectively dipping treatment; the first bath dipping liquid adopts water-based epoxy resin, dimethylpyrazole blocked isocyanate and an acidic metal oxidation catalyst, and the second bath dipping liquid adopts water-based mixture of zinc methacrylate or zinc acrylate and the like. The second bath dipping liquid adopts aqueous solution of RF resin produced by polycondensation reaction of resorcinol and furfural and mixed solution of one or more latices of VPL, NRL, CRL, SBRL. The ultra-high molecular weight polyethylene fiber treated by the method of the invention enhances the bonding performance of the interface between the fiber and rubber after being treated.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to an ultrahigh molecular weight polyethylene fiber reinforced material and a preparation method thereof.
Background
The three major high performance fibers in the world today are: aramid fibers, carbon fibers, ultra-high molecular weight polyethylene fibers are only produced in small quantities currently due to technical problems; carbon fibers are still in the test and primary production stages, and the product can only be applied to the fields of wear-resistant fillers and the like; the ultra-high molecular weight polyethylene fiber has high specific strength and high specific modulus, the specific strength is more than ten times that of steel wires with the same section, and the ultra-high molecular weight polyethylene fiber has a plurality of excellent characteristics, has great advantages in the high-performance fiber market, including the aspects from mooring ropes of offshore oil fields to high-performance light composite materials, and plays a very important role in the fields of modernized war, aviation, aerospace, sea area defense equipment and the like.
However, the surface of the ultra-high molecular weight polyethylene fiber lacks active chemical groups, so that the interface bonding performance is poor, and the interface mechanical property applied to the working condition environment is difficult to achieve.
Disclosure of Invention
The invention aims to provide an ultra-high molecular weight polyethylene fiber reinforced material and a preparation method thereof, wherein the ultra-high molecular weight polyethylene fiber is treated by dipping in a three-bath method, and the bonding performance of the interface between the treated fiber and rubber is enhanced.
The specific technical scheme of the invention is as follows:
the preparation process of superhigh molecular weight polyethylene fiber reinforced material includes three-bath process of dipping, including the first bath dipping, the second bath dipping and the third bath dipping;
the first bath dipping liquid comprises the following raw materials in parts by mass:
the acidic metal oxidation is selected from CrO 3 、Mn 2 O 7 、Tc 2 O 7 Or any one or 2 of OsO is compounded;
preferably CrO is used 3 、Mn 2 O 7 Compounding, wherein the mass ratio is 5-1:3-10, more preferably a mass ratio of 1:1;
the mass concentration of the dimethylpyrazole blocked isocyanate is 50%;
the mass concentration of the epoxy resin is 100%;
the mass concentration of the di (triethanolamine) diisopropyl titanate is 80%;
the preparation method of the first bath dipping liquid comprises the following steps: firstly, 1000 parts of deionized water is put into a reaction kettle, the diisopropyl di (triethanolamine) titanate with the formula amount is added, the stirring speed is 150 rpm, the stirring is carried out for 10 minutes, then the acidic metal oxide is added, and the stirring is continuously carried out for 1 hour; adding the formula amount of epoxy resin, stirring for 3 hours, adjusting the stirring speed to 60 revolutions per minute, adding dimethylpyrazole blocked isocyanate, stirring for 30 minutes, and stopping; and (5) standby.
The total mass concentration of the first bath gum dipping liquid is 3-5.5%, and the pH value is 3.5-5.5.
The second bath gum dipping solution comprises the following raw materials in parts by mass:
the preparation method of the second bath dipping liquid comprises the following steps: adding 500 parts of deionized water into a reaction kettle, controlling the water temperature to be 25-45 ℃, adding polyethylene glycol, stirring for 3-5 hours at a stirring speed of 20 r/min, adding zinc methacrylate or zinc acrylate in a formula amount after the polyethylene glycol is completely dissolved, and carrying out ultrasonic vibration on the mixed solution in the reaction kettle by adopting an ultrasonic instrument at a frequency of 40KHZ for 30 minutes to 1 hour; and finally, transferring the suspension liquid formed by the reaction to high-pressure spraying equipment for later use.
The total mass concentration of the second bath dipping liquid is 15-20%, and the pH value is 7.8-9.5.
The third bath gum dipping solution comprises the following raw materials in parts by mass:
the mass concentration of the pre-condensation resin is 75%;
the pre-condensed resin is a resorcinol-formaldehyde polymer (resorcinol-formaldehyde resin).
The mass concentration of the furfural solution is 50%;
the mass concentration of the emulsion is 40-50%; the latex is EPML, NBR, CR or SBR latex;
the preparation method of the third bath dipping liquid comprises the following steps:
A. adding deionized water in a formula amount into a reaction kettle, stirring at a stirring speed of 60 r/min, adding sodium hydroxide under stirring conditions, stirring for 10 min, adding pre-condensation resin, stirring for 30 min, adding furfural solution, adjusting the stirring speed to 30 r/min, controlling the reaction temperature to be not more than 30 ℃ at maximum, and reacting for 8-10 h;
B. and (3) adding the latex with the formula amount into another reaction kettle, transferring the mixed solution after the reaction in the step (A) into the reaction kettle containing the latex, continuously stirring for 1 hour, and standing for 12 hours at the stirring speed of 30 r/min to obtain the latex dipping solution.
The total mass concentration of the third bath gum dipping solution is 14-18%, and the pH value is 7.8-9.0.
The invention provides a preparation method of an ultra-high molecular weight polyethylene fiber reinforced material, which specifically comprises the following steps:
1) Conducting heat treatment after conducting first bath dipping liquid treatment and drying on the ultra-high molecular weight polyethylene fiber grey cloth;
2) Spraying and drying the second bath dipping liquid, and performing heat treatment;
3) And (3) dipping the glue solution in a third bath, drying and then carrying out heat treatment.
In the step 1), a gumming machine with 8 gas heating ovens is adopted, the grey cloth is led into a cloth storage rack after being put on the machine, then sequentially enters a first bath gumming tank to be treated by a first bath gumming liquid, the gum attaching amount is controlled to be 0.5% -2%, and the grey cloth enters a drying oven after being sized;
in step 1), the dipping speed of the first bath dipping solution treatment: 20-40 m/min;
in the step 1), the drying is carried out at the temperature of 100-130 ℃;
in step 1), the heat treatment: the temperature is 140-145 ℃ and the tension is 20KN-35KN.
The step 2) is specifically as follows: then the mixture enters a second bath high-pressure spraying device to spray second bath dipping liquid, the glue attaching amount is controlled to be 1-2%, and after drying, heat treatment is carried out;
in the step 2), the drying is carried out at the temperature of 80-130 ℃;
in the step 2), the heat treatment is carried out at 130-140 ℃ under the tension of 5KN-10KN.
The gum dipping amount in the step 3) is controlled to be 2-5%.
In the step 3), the drying is carried out at 110-130 ℃;
in step 3), the heat treatment temperature: 130-140 deg.c and tension 5-15 KN.
And 3) after the treatment, coiling and packaging the finished product.
The ultra-high molecular weight polyethylene fiber reinforced material provided by the invention is prepared by adopting the method.
The first bath dipping liquid adopts water-based epoxy resin, dimethylpyrazole blocked isocyanate and an acidic metal oxidation catalyst, and the acidic metal oxidation catalyst can be CrO 3 、Mn 2 O 7 、Tc 2 O 7 One or 2 of OsO. The second bath dope uses zinc methacrylate or a water-based mixture of zinc acrylate. The third bath dipping liquid adopts a pre-condensed resin, an aqueous solution of resin generated by the polycondensation reaction of furfural solution and a mixed solution of one or more latices VPL, NRL, CRL, SBRL.
In the invention, the acid metal oxidation catalyst of the first bath dipping liquid can remove the weak interface layer on the surface of the ultra-high molecular weight polyethylene at high temperature, thereby generating etching effect and increasing the infiltration degree of epoxy resin and isocyanate; the polyurethane is generated by the reaction of isocyanate and polyether alcohol after epoxy polymerization at high temperature, the deblocking minimum temperature of the adopted dimethylpyrazole blocked isocyanate is 130 ℃, and the deblocked isocyanate can fully react with epoxy and is coated on the surface of the fiber to form a stable bonding layer. Through the second bath dipping solution treatment, a layer of acrylic acid metal salt is further coated on the outer layer, and the metal salt can migrate into a rubber system in the subsequent rubber vulcanization process, so that rubber-metal ion bonds are formed between rubber and the previous acidic metal oxide at high temperature, and the bonding force between the rubber and a fiber interface is improved. And (3) dipping the phenolic resin-latex dipped layer on the outermost layer through a third bath of a third bath dipping liquid, wherein phenolic hydroxyl groups and epoxy groups in the phenolic resin can carry out ring opening reaction under the action of high temperature, and can also carry out crosslinking curing reaction with-NCO groups after isocyanate deblocking.
Compared with the prior art, the ultra-high molecular weight polyethylene fiber reinforced material can enhance the bonding performance with a rubber interface through three kinds of dipping liquid treatment.
Drawings
FIG. 1 is a graph showing the bonding of the ultra high molecular weight polyethylene fiber reinforced material and rubber of example 1;
FIG. 2 is a graph of the ultra high molecular weight polyethylene fiber reinforced material of example 2 after bonding to rubber;
FIG. 3 is a graph showing the bonding of the UHMWPE fiber reinforced material of example 3 to rubber;
FIG. 4 is a graph showing the bonding of the ultra high molecular weight polyethylene fiber reinforced material to rubber according to comparative example 1;
fig. 5 is a test chart of comparative example 2 after bonding the ultra high molecular weight polyethylene fiber reinforced material to rubber.
Detailed Description
Example 1
The preparation process of superhigh molecular weight polyethylene fiber reinforced material includes three-bath process of dipping, including the first bath dipping, the second bath dipping and the third bath dipping;
the total mass concentration of the first bath gum dipping is 4%, and the pH value is 5;
the total mass concentration of the second bath gum dipping is 18%, and the pH value is 9;
the total mass concentration of the third bath gum dipping is 16%, and the pH value is 9.
The first bath gum dipping comprises the following raw materials in parts by mass:
the preparation method of the first bath dipping liquid comprises the following steps: 1000 parts of deionized water is firstly placed in a reaction kettle according to parts by weight, diisopropyl di (triethanolamine) titanate is added, rapid stirring is carried out, the stirring speed is 150 revolutions per minute, stirring is carried out for 10 minutes, and then CrO is added 3 、Mn 2 O 7 Stirring was continued for about 1 hour. Then adding 1,2, 3-glycerol dehydrated glycerol ether, stirring for 3 hours, adjusting the stirring speed to 60 r/min, adding butanone oxime to seal isocyanate, stirring for 30 minutes, and stopping for standby.
The second bath gum dipping comprises the following raw materials in parts by mass:
deionized water: 500 parts of
Polyethylene glycol (molecular weight 2000): 10 parts of
Zinc methacrylate: 30 parts.
The preparation method of the second bath dipping liquid comprises the following steps: adding 500 parts of deionized water into a reaction kettle according to the parts by mass, controlling the water temperature at 35 ℃, adding polyethylene glycol, and stirring for 3 hours at a stirring speed of 20 revolutions per minute; after the polyethylene glycol is completely dissolved, zinc methacrylate is added, and the mixed solution in the reaction kettle is subjected to ultrasonic vibration by adopting an ultrasonic instrument, wherein the frequency is 40KHZ, and the processing time is 1 hour. And finally transferring the suspension liquid formed by the reaction to high-pressure spraying equipment.
The third bath gum dipping comprises the following raw materials in parts by mass:
the preparation method of the third bath gum dipping comprises the following steps:
A. adding deionized water into a reaction kettle, stirring at a stirring speed of 60 r/min, adding sodium hydroxide under stirring condition, stirring for 10 min, adding resorcinol-formaldehyde polymer, stirring for 30 min, adding furfural solution, adjusting stirring speed to 30 r/min, controlling the reaction temperature to be not more than 30 ℃ at maximum, and reacting for 8 h.
B. And (c) adding the CRL latex into another reaction kettle, and then transferring the mixed solution prepared in the step (A) into the reaction kettle, and continuously stirring for 1 hour at a stirring speed of 30 revolutions per minute. The mixed solution can be used as a dipping solution after being placed for 12 hours.
The method for preparing the ultra-high molecular weight polyethylene fiber reinforced material by using the first bath dipping liquid, the second bath dipping liquid and the third bath dipping liquid comprises the following steps:
1) And (3) conducting heat treatment after conducting first bath dipping liquid treatment and drying on the ultra-high molecular weight polyethylene fiber grey cloth:
the dipping machine adopts a dipping machine with 8 gas heating ovens, the grey cloth is guided into a cloth storage rack after being put on the machine, then sequentially enters a first bath dipping tank to be treated by a first bath dipping liquid, the gum attaching amount is controlled to be 1%, and the grey cloth enters a drying oven after sizing; dipping speed of the first bath dipping solution treatment: 30 m/min; the drying temperature is 120 ℃; the heat treatment temperature was 140℃and the tension was 30KN.
2) Spraying and drying the second bath dipping liquid, and then carrying out heat treatment: spraying the second bath dipping liquid in a second bath high-pressure spraying device, controlling the adhesive attaching amount to be 1.5%,
drying at 90 ℃; the heat treatment temperature was 140℃and the tension was 8KN.
3) And (3) dipping and drying the third bath dipping liquid, and then carrying out heat treatment: the gum dipping amount is controlled at 3.5%, and the drying temperature is 120 ℃; heat treatment temperature: 140 deg.c and 10KN tension.
4) And (5) coiling and packaging the finished product.
By adopting the formula and the process, the rubber compound is vulcanized and bonded with the rubber compound with the rubber formula shown in the table 1, and the rubber formula is shown in the table 1. The adhesive strength is based on the detection method standard: GB/T31334.1-2015; the breaking strength and the breaking elongation are as follows according to the detection method standard: GB/T31334.5-2017.
Table 1 rubber compound formulation
| Sequence number | Project | Mass per part |
| 1 | Natural rubber (No. 20 standard rubber) | 100.0 |
| 2 | Stearic acid | 2.0 |
| 3 | Zinc oxide (content ≡ 99.97%) | 4.0 |
| 4 | Anti-aging agent BLE | 0.8 |
| 5 | Aromatic oil | 3.0 |
| 6 | N660 carbon black | 35.0 |
| 7 | Sulfur, sulfur and its preparation method | 2.5 |
| 8 | Vulcanization accelerator M | 0.8 |
| 9 | Totalizing | 148.1 |
Example 2
The preparation process of superhigh molecular weight polyethylene fiber reinforced material includes three-bath process of dipping, including the first bath dipping, the second bath dipping and the third bath dipping;
the total mass concentration of the first bath gum dipping is 5.5%, and the pH value is 5;
the total mass concentration of the second bath gum dipping is 20%, and the pH value is 9.5;
the total mass concentration of the third bath gum dipping is 18%, and the pH value is 9.0.
The first bath gum dipping comprises the following raw materials in parts by mass:
the preparation method of the first bath dipping liquid comprises the following steps: 1000 parts of deionized water is firstly put into a reaction kettle, diisopropyl di (triethanolamine) titanate is added, rapid stirring is carried out, the stirring speed is 150 rpm, the stirring is carried out for 10 minutes, and then CrO is added 3 、Mn 2 O 7 Stirring was continued for 1 hour. Then adding 1,2, 3-glycerol dehydrated glycerol ether, stirring for 3 hours, adjusting the stirring speed to 60 revolutions per minute, adding butanone oxime to seal isocyanate, stirring for 30 minutes, and stopping for standby.
The second bath gum dipping comprises the following raw materials in parts by mass:
deionized water: 500 parts of
Polyethylene glycol (molecular weight 2000): 12 parts of
Zinc acrylate: 35 parts.
The preparation method of the second bath dipping liquid comprises the following steps: 500 parts of deionized water is added into a reaction kettle, the water temperature is controlled at 45 ℃, polyethylene glycol is added, and the stirring is carried out for 4 hours at a stirring speed of 20 revolutions per minute. After the polyethylene glycol is completely dissolved, zinc acrylate is added, and ultrasonic oscillation is carried out on the mixed solution in the reaction kettle by adopting an ultrasonic instrument, wherein the frequency is 40KHZ, and the processing time is 45min. And finally transferring the suspension liquid formed by the reaction to high-pressure spraying equipment for standby.
The third bath gum dipping comprises the following raw materials in parts by mass:
the preparation method of the third bath gum dipping comprises the following steps:
A. adding deionized water into a reaction kettle, adding sodium hydroxide, stirring for 10 minutes at a stirring speed of 60 revolutions per minute, adding resorcinol-formaldehyde polymer, stirring for 30 minutes, adding furfural solution, adjusting the stirring speed to 30 revolutions per minute, controlling the reaction temperature to be not more than 30 ℃ at the maximum, and reacting for 8 hours.
B. The latex was added to another reactor, and then the mixed solution after the completion of the reaction was transferred to the reactor, and stirring was continued for 1 hour at a stirring speed of 30 rpm. The mixed solution can be used as a dipping solution after being placed for 12 hours.
The method for preparing the ultra-high molecular weight polyethylene fiber reinforced material by using the first bath dipping liquid, the second bath dipping liquid and the third bath dipping liquid comprises the following steps: 1) And (3) conducting heat treatment after conducting first bath dipping liquid treatment and drying on the ultra-high molecular weight polyethylene fiber grey cloth:
the dipping machine adopts a dipping machine with 8 gas heating ovens, the grey cloth enters a cloth storage frame after being put on the machine, then enters a first bath dipping tank to be treated by a first bath dipping liquid, the gum attaching amount is controlled at 1%, and the dipping speed of the first bath dipping liquid treatment is controlled to be as follows: 35 m/min; the drying temperature is 110 ℃; the heat treatment temperature was 140℃and the tension was 25KN.
2) Spraying and drying the second bath dipping liquid, and then carrying out heat treatment: spraying the second bath dipping liquid in a second bath high-pressure spraying device, wherein the adhesive attaching amount is controlled to be 1.5%, and the drying temperature is 100 ℃; the heat treatment temperature is 130 ℃ and the tension is 6KN.
3) And (3) dipping and drying the third bath dipping liquid, and then carrying out heat treatment: the gum dipping amount is controlled at 4 percent, and the drying temperature is 115 ℃; heat treatment temperature: 135 deg.c and 12KN tension.
4) And (5) coiling and packaging the finished product.
The test was performed in the same manner and with the rubber as in example 1.
Example 3
The preparation process of superhigh molecular weight polyethylene fiber reinforced material includes three-bath process of dipping, including the first bath dipping, the second bath dipping and the third bath dipping;
the total mass concentration of the first bath gum dipping is 3%, and the pH value is 4;
the total mass concentration of the second bath gum dipping is 16%, and the pH value is 8.5;
the total mass concentration of the third bath gum dipping is 14%, and the pH value is 8.5.
The first bath gum dipping comprises the following raw materials in parts by mass:
the preparation method of the first bath dipping liquid comprises the following steps: 1000 parts of deionized water is firstly put into a reaction kettle, diisopropyl di (triethanolamine) titanate is added, rapid stirring is carried out, the stirring speed is 150 rpm, the stirring is carried out for 10 minutes, and then CrO is added 3 、Mn 2 O 7 Stirring was continued for 1 hour; then adding 1,2, 3-glycerol dehydrated glycerol ether, stirring for 3 hours, adjusting the stirring speed to 60 r/min, adding butanone oxime to seal isocyanate, stirring for 30 minutes, and stopping for standby.
The second bath gum dipping comprises the following raw materials in parts by mass:
deionized water: 500 parts of
12 parts of polyethylene glycol (molecular weight 2000)
Zinc acrylate: 30 parts.
The preparation method of the second bath dipping liquid comprises the following steps: 500 parts of deionized water is added into a reaction kettle, the water temperature is controlled at 30 ℃, polyethylene glycol is added, and the stirring is carried out for 4.5 hours at a stirring speed of 20 revolutions per minute. After the polyethylene glycol is completely dissolved, zinc acrylate is added, and ultrasonic oscillation is carried out on the mixed solution in the reaction kettle by adopting an ultrasonic instrument, wherein the frequency is 40KHZ, and the processing time is 1 hour. And finally transferring the suspension liquid formed by the reaction to high-pressure spraying equipment.
The third bath gum dipping comprises the following raw materials in parts by mass:
the preparation method of the third bath gum dipping comprises the following steps:
A. adding deionized water into a reaction kettle, adding sodium hydroxide, stirring for 10 minutes at a stirring speed of 60 revolutions per minute, adding pre-condensed resin, stirring for 30 minutes, adding furfural solution, adjusting the stirring speed to 30 revolutions per minute, and controlling the reaction temperature to be not more than 30 ℃ at the maximum, wherein the reaction time is 9 hours.
B. The latex was added to another reactor, and then the mixed solution after the completion of the reaction was transferred to the reactor, and stirring was continued for 1 hour at a stirring speed of 30 rpm. The mixed solution can be used as a dipping solution after being placed for 12 hours.
The method for preparing the ultra-high molecular weight polyethylene fiber reinforced material by using the first bath dipping liquid, the second bath dipping liquid and the third bath dipping liquid comprises the following steps: 1) And (3) conducting heat treatment after conducting first bath dipping liquid treatment and drying on the ultra-high molecular weight polyethylene fiber grey cloth:
the dipping machine adopts a dipping machine with 8 gas heating ovens, the grey cloth is guided into a cloth storage rack after being put on the machine, then sequentially enters a first bath dipping tank to be treated by a first bath dipping liquid, the gum attaching amount is controlled to be 1.5 percent, and the grey cloth enters a drying oven after sizing; dipping speed of the first bath dipping solution treatment: 35 m/min; the drying temperature is 115 ℃; the heat treatment temperature was 145℃and the tension 28KN.
2) Spraying and drying the second bath dipping liquid, and then carrying out heat treatment: spraying the second bath dipping liquid in a second bath high-pressure spraying device, wherein the adhesive attaching amount is controlled to be 1%, and the drying temperature is 80 ℃; the heat treatment temperature is 135 ℃ and the tension is 10KN.
3) And (3) dipping and drying the third bath dipping liquid, and then carrying out heat treatment: the gum dipping amount is controlled at 2.5 percent, and the drying temperature is 125 ℃; heat treatment temperature: 140 deg.c and 13KN tension.
4) And (5) coiling and packaging the finished product.
The test was performed in the same manner and with the rubber as in example 1.
Comparative example 1
A dipping solution of ultra-high molecular weight polyethylene fiber reinforced material is prepared by the following steps:
1) The reaction kettle is put into deionized water 150 parts by weight, 0.3 part of sodium hydroxide is added and stirred for 10 minutes, the stirring speed is 60 turns/minute, then 10 parts of resorcinol is added and stirred for 30 minutes, then 15 parts of formaldehyde solution (37% mass concentration) is added, the stirring speed is adjusted to 30 turns/minute, the reaction temperature is controlled to be not more than 28 ℃ at maximum, and the reaction time is 5 hours.
2) 80 parts of deionized water, 240 parts of VPL latex, and stirring for 10 minutes at a stirring speed of 60 rpm were added to another reaction vessel, and then the mixed solution after the completion of the reaction was transferred to the reaction vessel, and stirring was continued for 1 hour at a stirring speed of 30 rpm. The mixed solution can be used as a dipping solution after being placed for 12 hours.
The dipping solution is used for treating ultra-high molecular weight polyethylene fibers, and comprises the following specific production steps: the ultra-high molecular weight polyethylene fiber grey cloth is fed into a cloth storage rack after being fed into a machine, then fed into a gum dipping tank, and the fiber surface is sized and then is subjected to drying, stretching heat treatment, shaping heat treatment, product coiling and packaging. The specific process parameters are set as follows:
dipping speed: 20-40 m/min;
the pre-drying temperature is 80-100 ℃, the post-drying temperature is 100-120 ℃, and the stretching heat treatment temperature is as follows: 140-145 ℃ and 20-35 KN of tension; setting heat treatment temperature: 130-140 deg.c and tension 5-15 KN. By adopting the formula and the process, the rubber is vulcanized and bonded with the rubber compound, and the rubber formula is shown in table 1.
The product was tested in the same way and with rubber as in example 1.
Comparative example 2
A dipping solution of ultra-high molecular weight polyethylene fiber reinforced material is prepared by the following steps:
the preparation method of the first bath dipping liquid comprises the following steps: a certain amount of deionized water 1000 parts is firstly put into a reaction kettle, then 30 parts of 1,2, 3-glycerol dehydrated glycerol ether is added, stirring is carried out for 3 hours at the stirring speed of 60 revolutions per minute, then 90 parts of butanone oxime blocked isocyanate is added, and stirring is carried out for 30 minutes and then the reaction kettle is stopped for standby.
The preparation method of the second bath dipping liquid comprises the following steps:
1) 150 parts of deionized water is put into a reaction kettle, 0.3 part of sodium hydroxide is added and stirred for 10 minutes, the stirring speed is 60 revolutions per minute, 10 parts of resorcinol is added and stirred for 30 minutes, 15 parts of formaldehyde solution (37% mass concentration) is added, the stirring speed is adjusted to 30 revolutions per minute, the reaction temperature is controlled to be not more than 28 ℃ at maximum, and the reaction time is 5 hours.
2) 80 parts of deionized water, 240 parts of VPL latex, and stirring for 10 minutes at a stirring speed of 60 rpm were added to another reaction vessel, and then the mixed solution after the reaction in step 1) was transferred to the reaction vessel, and stirring was continued for 1 hour at a stirring speed of 30 rpm. The mixed solution can be used as a second bath dip after being left for 12 hours.
The dipping solution is used for treating ultra-high molecular weight polyethylene fibers, and comprises the following specific production steps: the ultra-high molecular weight polyethylene fiber grey cloth is guided into a cloth storage rack after being put on a machine, then enters a first bath gum dipping tank, and is dried and heat treated: dipping speed: 30 m/min; the bath drying temperature is 100-120 ℃, and the stretching heat treatment temperature is as follows: 140-145 ℃ and 20-35 KN of tension; then the mixture enters a second gum dipping tank for drying and heat treatment: the two-bath drying temperature is 80-100 ℃; setting heat treatment temperature: 130-140 deg.c and tension 5-15 KN. And finally, coiling and packaging.
The product was tested in the same way and with rubber as in example 1.
The product properties tested in each example and comparative example are shown in Table 2.
Table 2 performance indicators for examples and comparative examples
From fig. 1 to fig. 3, it can be seen that after the ultra-high molecular weight polyethylene fibers treated by the method are respectively treated by three-bath dipping with different formulas, the rubber cohesive failure is large-area after the test by adopting a specified method, and the reinforcing material and the rubber can form good crosslinking reaction after vulcanization. From fig. 1, it can be seen that the area of the rubber covered with the fiber is almost 100%, which means that the ultra-high molecular weight polyethylene fiber can form a very sufficient crosslinking reaction with the rubber after vulcanization after the impregnation treatment by the three-bath formulation.
As can be seen from fig. 4 to fig. 5, after the ultra-high molecular weight polyethylene fibers are respectively dipped by the method in the comparative example, the interface between the rubber and the reinforcing material is destroyed in a large area after being tested by a specified method, which indicates that the reinforcing material and the rubber cannot form better crosslinking reaction after being vulcanized.
Claims (8)
1. The preparation method of the ultra-high molecular weight polyethylene reinforced material is characterized by comprising a three-bath dipping method, wherein the first bath dipping liquid, the second bath dipping liquid and the third bath dipping liquid are used for respectively dipping; the first bath dipping liquid comprises the following raw materials in parts by mass:
the acidic metal oxide adopts CrO 3 And Mn of 2 O 7 Is a combination of (a);
the epoxy resin is 1,2, 3-glycerol dehydrated glycerol ether;
the second bath gum dipping solution comprises the following raw materials in parts by mass:
deionized water 500 parts
10-12 parts of polyethylene glycol
30-35 parts of zinc methacrylate or zinc acrylate;
the third bath gum dipping solution comprises the following raw materials in parts by mass:
the precondensate resin is resorcinol-formaldehyde polymer.
2. The method of preparing the first bath dope according to claim 1, wherein the method of preparing the first bath dope is: firstly, adding deionized water with a formula amount into a reaction kettle, adding diisopropyl di (triethanolamine) titanate with the formula amount, stirring, then adding acid metal oxide, and continuously stirring; then adding the formula amount of epoxy resin, reducing the stirring speed, continuing stirring, adding butanone oxime to seal isocyanate, and stirring; and (5) standby.
3. The preparation method according to claim 1 or 2, characterized in that the preparation method of the second bath dope is: adding deionized water with the formula amount into a reaction kettle, controlling the water temperature to be 25-45 ℃, adding polyethylene glycol, stirring for 3-5 hours, adding zinc methacrylate or zinc acrylate with the formula amount after the polyethylene glycol is completely dissolved, carrying out ultrasonic vibration on the mixed solution in the reaction kettle by adopting an ultrasonic instrument, and finally transferring the suspension liquid formed by the reaction to high-pressure spraying equipment for later use.
4. The preparation method according to claim 1, wherein the preparation method of the third bath dope is:
A. adding deionized water in a formula amount into a reaction kettle, adding sodium hydroxide under stirring, adding pre-condensed resin, stirring, adding furfural solution, reducing stirring speed, controlling the reaction temperature to be not more than 30 ℃ at maximum, and reacting for 8-10 hours;
B. and C, adding the latex with the formula amount into another reaction kettle, transferring the mixed solution after the reaction in the step A into the reaction kettle containing the latex, continuously stirring, and standing to obtain the latex serving as a dipping solution.
5. The preparation method according to claim 1, characterized in that it comprises in particular the following steps:
1) Conducting heat treatment after conducting first bath dipping liquid treatment and drying on the ultra-high molecular weight polyethylene fiber grey cloth;
2) Spraying and drying the second bath dipping liquid, and performing heat treatment;
3) Dipping in the third bath dipping solution, drying and then carrying out heat treatment;
in the step 1), the drying is carried out at the temperature of 100-130 ℃; the heat treatment: the temperature is 140-145 ℃ and the tension is 20KN-35KN.
6. The method according to claim 5, wherein in step 2), the drying is performed at a drying temperature of 80 to 130 ℃; the temperature of the heat treatment is 130-140 ℃ and the tension is 5KN-10KN.
7. The method of claim 5 or 6, wherein the drying in step 3) is performed at a temperature of 110-130 ℃; the heat treatment temperature: 130-140 deg.c and tension 5-15 KN.
8. An ultra-high molecular weight polyethylene reinforcement material prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111346951.0A CN113957717B (en) | 2021-11-15 | 2021-11-15 | Ultrahigh molecular weight polyethylene fiber reinforced material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111346951.0A CN113957717B (en) | 2021-11-15 | 2021-11-15 | Ultrahigh molecular weight polyethylene fiber reinforced material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113957717A CN113957717A (en) | 2022-01-21 |
| CN113957717B true CN113957717B (en) | 2023-05-23 |
Family
ID=79470400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111346951.0A Active CN113957717B (en) | 2021-11-15 | 2021-11-15 | Ultrahigh molecular weight polyethylene fiber reinforced material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113957717B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115522386A (en) * | 2022-10-25 | 2022-12-27 | 重庆国际复合材料股份有限公司 | Ultra-high molecular weight polyethylene fiber sizing agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108049185A (en) * | 2018-02-13 | 2018-05-18 | 山东星宇手套有限公司 | A kind of oiliness PU- butyronitrile two-layer compound rubber gloves and its manufacturing method |
| CN110713640A (en) * | 2018-07-13 | 2020-01-21 | 杭州星庐科技有限公司 | Rubber composition and processing method, and rubber product and production method using same |
| CN113355916A (en) * | 2021-06-22 | 2021-09-07 | 江苏恒神股份有限公司 | Carbon fiber bundling agent, carbon fiber bundle for winding forming, and preparation method and application thereof |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2750464B2 (en) * | 1990-01-30 | 1998-05-13 | 日本ゼオン株式会社 | Method for producing fiber-rubber composite |
| JP3812747B2 (en) * | 2004-05-18 | 2006-08-23 | 東洋紡績株式会社 | Polyester cord for rubber reinforcement and method for producing the same |
| WO2005111297A1 (en) * | 2004-05-18 | 2005-11-24 | Toyo Boseki Kabushiki Kaisha | Reinforcement polyester cords for rubbers and process for production thereof |
| EP1854917A4 (en) * | 2005-03-03 | 2010-03-17 | Toyo Boseki | Reinforcing polyester cord for rubbers and process for production thereof |
| KR101428602B1 (en) * | 2006-03-03 | 2014-09-11 | 인드스펙 케미칼 코포레이션 | Resorcinol resin-blocked isocyanates and their applications |
| CN101717645A (en) * | 2009-11-17 | 2010-06-02 | 张�林 | Etching plaster for metal and metal oxide transparent conducting layer and etching process |
| ES2623132T3 (en) * | 2012-12-13 | 2017-07-10 | Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi | An immersion material for lace fabrics and a production method thereof |
| EP2955268A1 (en) * | 2014-06-12 | 2015-12-16 | Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi | Dipping solution for cord fabrics |
| JP6623831B2 (en) * | 2016-02-25 | 2019-12-25 | 東レ株式会社 | Organic fiber cord and rubber products |
| CN107700220A (en) * | 2017-10-18 | 2018-02-16 | 江苏太极实业新材料有限公司 | A kind of preparation method of fibre framework materials dipping solution |
| CN110387744A (en) * | 2018-04-19 | 2019-10-29 | 北京化工大学 | A kind of fibre framework materials dipping solution, preparation method and dipping method |
| CN109097993A (en) * | 2018-09-10 | 2018-12-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
| CN110258117A (en) * | 2019-06-04 | 2019-09-20 | 安徽华烨特种材料有限公司 | A kind of ultra-high molecular weight polyethylene impregnated fabric and preparation method thereof |
| CN112064358A (en) * | 2019-06-10 | 2020-12-11 | 北京化工大学 | Environment-friendly impregnation system for fiber surface treatment, preparation method and impregnation method |
| CN112176729A (en) * | 2019-07-03 | 2021-01-05 | 北京化工大学 | Nano-reinforced environment-friendly impregnation system for fiber surface treatment, preparation method and impregnation method |
| CN110511459A (en) * | 2019-09-02 | 2019-11-29 | 北京化工大学 | A kind of fibre framework materials dipping solution, preparation method and dipping method |
| CN110952333A (en) * | 2019-10-21 | 2020-04-03 | 芜湖华烨新材料有限公司 | Production process of ultrahigh molecular weight polyethylene fiber rubber framework material |
| CN111395001B (en) * | 2020-03-30 | 2023-06-16 | 联新（开平）高性能纤维有限公司 | Conductive dipping liquid and preparation method and application thereof, dipping cord and preparation method and application thereof |
| CN113372642A (en) * | 2021-06-30 | 2021-09-10 | 北京冬曦既驾科技咨询有限公司 | Antibacterial toughening type polyethylene film and preparation method thereof |
-
2021
- 2021-11-15 CN CN202111346951.0A patent/CN113957717B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108049185A (en) * | 2018-02-13 | 2018-05-18 | 山东星宇手套有限公司 | A kind of oiliness PU- butyronitrile two-layer compound rubber gloves and its manufacturing method |
| CN110713640A (en) * | 2018-07-13 | 2020-01-21 | 杭州星庐科技有限公司 | Rubber composition and processing method, and rubber product and production method using same |
| CN113355916A (en) * | 2021-06-22 | 2021-09-07 | 江苏恒神股份有限公司 | Carbon fiber bundling agent, carbon fiber bundle for winding forming, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113957717A (en) | 2022-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6111204B2 (en) | Pneumatic radial tire | |
| Zhang et al. | Polyester (PET) fabrics coated with environmentally friendly adhesive and its interface structure and adhesive properties with rubber | |
| CN108431328B (en) | Polyester fiber, method for preparing the same, and tire cord comprising the same | |
| CN113957717B (en) | Ultrahigh molecular weight polyethylene fiber reinforced material and preparation method thereof | |
| JPS63327A (en) | Adhesion of rubber to aramid code | |
| CN110511459A (en) | A kind of fibre framework materials dipping solution, preparation method and dipping method | |
| CN112064358A (en) | Environment-friendly impregnation system for fiber surface treatment, preparation method and impregnation method | |
| JP2013076186A (en) | Manufacturing method of polyester fiber cord for rubber reinforcement and tire | |
| CN112878046A (en) | Pretreatment liquid for dipping aramid fiber hard cord and dipping method of aramid fiber hard cord | |
| WO2022137908A1 (en) | Adhesive composition for organic fibers, organic fiber-rubber composite body, and tire | |
| CN115431447B (en) | Method for enhancing interfacial adhesion strength of NR/SBR compound and polyester cord | |
| WO2021220989A1 (en) | Adhesive composition for organic fiber cords, organic fiber cord-rubber composite body, and tire | |
| WO2022065206A1 (en) | Adhesive composition for rubber/resin bonding, organic-fiber-cord/rubber composite, and tire | |
| CN116253987A (en) | Aqueous polyurethane emulsion, biodegradable glove and preparation method and application thereof | |
| JP5631800B2 (en) | tire | |
| CN108864515B (en) | Aminolysis-resistant dipping solution for polyester dipping canvas for high-temperature-resistant conveying belt and preparation method thereof | |
| JPS6310751B2 (en) | ||
| KR101898520B1 (en) | Cellulose fiber, method for preparing the same and tire cord including the same | |
| WO2022137703A1 (en) | Adhesive composition for organic fiber, organic fiber/rubber composite, and tire | |
| WO2016043395A1 (en) | Polyester fiber, method for preparing same, and tire code comprising same | |
| EP2931778A1 (en) | A spinfinish material applied on the fiber and a production method thereof | |
| CN114630861A (en) | Adhesion promoting composition for textile materials and related reinforced textile materials | |
| JP2012214136A (en) | Run-flat tire | |
| CN117468235A (en) | Water cement of water cement rope and use method thereof | |
| TW202405110A (en) | Adhesive composition, rubber reinforcing material and articles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |