CN113652039B - High-temperature-resistant and tough PVC cable material and preparation method thereof - Google Patents
High-temperature-resistant and tough PVC cable material and preparation method thereof Download PDFInfo
- Publication number
- CN113652039B CN113652039B CN202110975285.0A CN202110975285A CN113652039B CN 113652039 B CN113652039 B CN 113652039B CN 202110975285 A CN202110975285 A CN 202110975285A CN 113652039 B CN113652039 B CN 113652039B
- Authority
- CN
- China
- Prior art keywords
- parts
- castor oil
- temperature
- cable material
- pvc cable
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
The invention discloses a high-temperature-resistant and tough PVC cable material and a preparation method thereof, and belongs to the technical field of cable materials. The PVC cable material comprises the following raw materials in parts by weight: 90-120 parts of PVC resin, 14-22 parts of chloroprene rubber, 8-15 parts of modified castor oil based plasticizer, 2.5-6.5 parts of acid etched glass fiber, 1-2 parts of silane coupling agent, 1.5-5.5 parts of anti-aging agent, 2-4 parts of composite stabilizer and 1.5-3 parts of lubricant. The modified castor oil-based plasticizer takes castor oil as a base material, is grafted with a phosphorus-nitrogen flame retardant, belongs to a plant oil-based toughening agent, is harmless to a human body, and has small mobility.
Description
Technical Field
The invention belongs to the technical field of cable materials, and particularly relates to a high-temperature-resistant and tough PVC cable material and a preparation method thereof.
Background
With the rapid development of the wire and cable industry, the demand of the wire and cable is gradually increased, and the application is more and more extensive. The base material of the electric wire and the electric cable is mainly PVC plastic, the PVC plastic is one of five common synthetic plastics and is the second plastic variety which is only second to polyethylene in the world at present. The PVC cable material is particles prepared by taking polyvinyl chloride as basic resin, adding additives such as a stabilizer, a plasticizer, an inorganic filler, an auxiliary agent, a lubricant and the like, and mixing, kneading and extruding.
However, the PVC cable material has poor high temperature resistance and low toughness, which affects the service life of the cable and greatly limits the use occasions of the PVC cable. And the PVC wire and cable has the potential safety hazard of flammability at high temperature, so that power interruption is easily caused, and unnecessary economic loss is caused. Therefore, modifying the PVC cable material is a technical problem to be solved urgently by those skilled in the art
For example, the Chinese patent CN110218402B discloses a high-temperature resistant flame-retardant PVC cable material and a preparation method thereof, wherein the PVC cable material comprises the following raw material components in parts by weight: the PVC cable material provided by the invention has the advantages of excellent high temperature resistance, weather resistance and flame retardant property, and comprises, by weight, 200 parts of PVC resin, 20-30 parts of triethyl citrate, 10-20 parts of silicon-containing diphenylamine, 30-50 parts of chloroprene rubber, 6-12 parts of phosphorus-nitrogen doped single-walled carbon nanotubes, 2-4 parts of a lubricant, 1-3 parts of a plasticizer, 2-3 parts of an antioxidant and 2-4 parts of a stabilizer. However, the plasticizer added in the PVC cable material provided by the invention is diisodecyl phthalate, and researches show that the o-benzene plasticizer can enter human bodies through various ways such as oral administration, respiratory tract, intravenous infusion, skin absorption and the like, has toxic effect on a plurality of systems of organisms, is considered as an environmental endocrine interference factor, is a low molecular weight compound or polymer mostly, and is easy to migrate in the subsequent use function process of the PVC cable, so that the toughness of the PVC cable is finally deteriorated, and the use of the PVC cable is influenced.
Therefore, the invention provides a high-temperature-resistant and tough PVC cable material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant and tough PVC cable material and a preparation method thereof.
The technical problems to be solved by the invention are as follows: the toughness of the existing PVC cable is easy to become poor after use.
The purpose of the invention can be realized by the following technical scheme:
a high-temperature-resistant and tough PVC cable material comprises the following raw materials in parts by weight: 90-120 parts of PVC resin, 14-22 parts of chloroprene rubber, 8-15 parts of modified castor oil based plasticizer, 2.5-6.5 parts of acid etched glass fiber, 1-2 parts of silane coupling agent, 1.5-5.5 parts of anti-aging agent, 2-4 parts of composite stabilizer and 1.5-3 parts of lubricant.
Further, the modified castor oil-based plasticizer is prepared by the following steps:
A. adding anhydrous castor oil, sodium methoxide and triethanolamine into a reaction kettle provided with a mechanical stirrer and a condenser, heating to 200 ℃ under stirring, keeping the temperature and introducing nitrogen for 30min, then adding glycerol, reacting at 180-200 ℃ for 3h, cooling to room temperature, washing with water for three times, drying with anhydrous sodium sulfate, and filtering to obtain castor oil polyol, wherein the molar ratio of the anhydrous castor oil to the glycerol is 1: 1.5-2, the total adding mass of the sodium methoxide and the triethanolamine is 0.5-0.8% of the adding mass of the castor oil, and the mass ratio of the sodium methoxide to the triethanolamine is 1: 2;
B. adding castor oil polyalcohol, glacial acetic acid and phosphoric acid into a round-bottom flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, after uniform mixing, dropwise adding hydrogen peroxide by using the constant-pressure dropping funnel, wherein the dropping speed is 1-2 drops/second, after dropping, stirring and reacting for 5 hours at 55 ℃, then washing to neutrality by using distilled water, and carrying out reduced pressure distillation at 60 ℃ to obtain epoxy castor oil, wherein the mass ratio of castor oil, glacial acetic acid, phosphoric acid and hydrogen peroxide is 100: 20-50: 1-2: 80-100 parts of;
C. mixing epoxy castor oil, a flame retardant containing hydroxyl phosphorus and nitrogen and toluene, adding a potassium hydroxide flaky solid, reacting at 90 ℃ for 6 hours, washing to be neutral, distilling under reduced pressure, and drying at 55 ℃ in vacuum to constant weight to obtain an intermediate 1, wherein the molar ratio of the epoxy castor oil to the flame retardant containing hydroxyl phosphorus and nitrogen is 1: 3.1 to 3.2 percent, wherein the added mass of the potassium hydroxide flaky solid is 0.5 to 1.5 percent of the mass of the hydroxyl-containing phosphorus-nitrogen flame retardant; adding the intermediate 1 and acetic anhydride into a three-neck round-bottom flask provided with a thermometer, a stirrer and a condenser, stirring and mixing uniformly, then stirring and reacting at 140 ℃ for 1.5h, cooling, washing to be neutral by using distilled water, and carrying out reduced pressure distillation at 55 ℃ to obtain the modified castor oil based plasticizer, wherein the mass ratio of the intermediate 1 to the acetic anhydride is 100: 80-100.
In the step A, castor oil polyol generated by castor oil and glycerol under sodium methoxide and triethanolamine is mixed alcohol, and the corresponding molecular structural formula is shown in the specification
In the step B, the castor oil polyalcohol is epoxidized under the action of mixed acid and hydrogen peroxide to correspondingly generate mixed epoxidized castor oil, in the step C, the mixed epoxidized castor oil is reacted with the hydroxyl-containing phosphorus-nitrogen flame retardant, the reaction of epoxy group and phenolic hydroxyl group is utilized to graft the castor oil and the phosphorus-nitrogen flame retardant to obtain an intermediate 1, and then the esterification reaction of the intermediate 1 and acetic anhydride is utilized to generate the modified castor oil based plasticizer, so that the plasticizer is a mixture, and the corresponding molecular structural formula is shown in the specification
In the reaction step, the castor oil and the glycerol are selected to react to form the mixed polyol, so that three arms of the castor oil are subjected to one-arm reaction and two-arm reaction, the steric effect of the subsequent reaction of the epoxy castor oil and the hydroxyl-containing phosphorus-nitrogen flame retardant is reduced, and the reaction efficiency of the epoxy castor oil and the hydroxyl-containing phosphorus-nitrogen flame retardant is improved; the produced modified castor oil-based plasticizer takes castor oil as a base material, belongs to a plant oil-based plasticizer and is harmless to human bodies, the relative molecular mass of the modified castor oil-based plasticizer is larger than that of an o-benzene plasticizer, the mobility is small, and the modified castor oil-based plasticizer is grafted with a phosphorus-nitrogen flame retardant which is added into a PVC cable base material, so that the plasticity and toughness of the PVC base material can be improved, and the high temperature resistance of the PVC cable material can be improved.
Further, the hydroxyl-containing phosphorus-nitrogen flame retardant is prepared by the following steps:
a11, uniformly mixing aniline derivatives, triethylamine and dry chloroform in an ice water bath, dropwise adding a chloroform solution of diphenyl chlorophosphate at 0 ℃ at a dropping speed of 1 drop/second, reacting at a constant temperature for 5 hours, removing the ice water bath, heating to room temperature, continuing to react for 12 hours, then removing the solvent by vacuum distillation, washing with 0 ℃ distilled water for 2-3 times, finally recrystallizing with tetrahydrofuran, and drying in vacuum to obtain an intermediate 2, wherein the molar ratio of the aniline derivatives to the triethylamine to the diphenyl chlorophosphate is 1: 2.2-2.5: 2.2-2.5;
the molecular structural formula of the intermediate 2 is as follows:
a12, adding the intermediate 2 and pyridine into a three-neck flask with a stirrer and a reflux device, introducing nitrogen for 30min, then adding a volume fraction of 10% Pd/C catalyst, introducing hydrogen, stirring and reacting at room temperature under the protection of hydrogen for 24h, finishing the reaction, filtering, washing with methanol for 3 times, combining filtrates, and distilling the filtrate under reduced pressure at room temperature to obtain the hydroxyl-containing phosphorus-nitrogen flame retardant, wherein the dosage ratio of the intermediate 2, pyridine and Pd/C catalyst is 0.1 mmol: 30-80 mL: 0.1-0.3 g.
The molecular structural formula of the hydroxyl-containing phosphorus-nitrogen flame retardant is as follows:
in the step A11, triethylamine is used as an acid-binding agent, amino groups in aniline derivatives react with diphenyl chlorophosphate to generate an intermediate 2, namely a phosphorus-nitrogen compound, and then in the step A12, debenzylation reaction of a benzyl ether structure in the intermediate 2 is utilized to generate the hydroxyl-containing phosphorus-nitrogen flame retardant.
Further, the aniline derivative is prepared by the following steps:
x1, adding 4-hydroxybenzaldehyde, nickel acetate and glacial acetic acid into a round-bottom flask provided with a stirrer and a thermometer, stirring and mixing uniformly, then dropwise adding benzyl chloride by using a constant-pressure funnel at a dropping speed of 1-2 drops/second, after the dropwise adding is completed, carrying out reflux reaction at 130 ℃ for 3 hours, finishing the reaction, cooling to 50 ℃, carrying out reduced pressure rotary evaporation, adsorbing nickel acetate by using activated carbon, filtering, washing with water, and drying to obtain an intermediate 3, wherein the molar ratio of the 4-hydroxybenzaldehyde to the benzyl chloride is controlled to be 1: 1, adding nickel acetate with the mass accounting for 1-3% of the mass of the 4-hydroxybenzaldehyde;
the molecular structural formula of the intermediate 3 is shown as follows:
x2, adding the intermediate 3, aniline and aniline hydrochloride into a four-neck flask with a stirrer and a nitrogen introducing device, uniformly stirring, heating to 110 ℃, reacting at constant temperature for 2 hours, heating to 148 ℃, continuing to react at constant temperature for 1.5 hours, cooling to 55 ℃, distilling under reduced pressure for 30min after the reaction is finished, adding 2mol/L diluted hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with 2mol/L diluted sodium hydroxide solution until the pH value is 7-8, generating a precipitate at the moment, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3-5 times, recrystallizing the crude product with ethanol/water for two times, and finally drying in vacuum at 60 ℃ for 24 hours to obtain an aniline derivative, wherein the dosage ratio of the intermediate 3, aniline and aniline hydrochloride is 0.1 mol: 0.11-0.13 mol: 4-6 mL.
The molecular structure of the aniline derivative is as follows:
in the X1 step, the catalytic action of nickel acetate is utilized to increase the structure of benzyl ether on 4-hydroxybenzaldehyde to generate an intermediate product 3-benzyl ether benzaldehyde, and in the X2 step, aldehyde group and aniline are utilized to perform addition reaction under the action of aniline hydrochloride to produce an aniline derivative, wherein the aniline derivative has a symmetrical aniline structure and a benzyl ether structure, the aniline structure is convenient to react with diphenyl chlorophosphate, and the benzyl ether structure is convenient to generate hydroxyl.
Therefore, when the structure of the aniline derivative is designed and synthesized for generating the hydroxyl-containing phosphorus-nitrogen flame retardant, firstly, the introduction of benzyl reduces the occurrence of side reactions during the reaction of the aniline derivative and diphenyl chlorophosphate, and because phenolic hydroxyl can also react with diphenyl chlorophosphate in the presence of an acid binding agent, but is protected by benzyl, the produced benzyl ether structure cannot react with diphenyl chlorophosphate, secondly, the phenolic hydroxyl is protected to avoid the reaction of hydroxyl, and the debenzylation protection is carried out to obtain the phenolic hydroxyl again, so that the reaction of the phenolic hydroxyl and an epoxy group, namely the reaction of the hydroxyl-containing phosphorus-nitrogen flame retardant and epoxy castor oil is utilized.
Further, the specific acid etching method for acid etching glass fiber refers to journal, journal of "journal of composite Material", volume 28, No. 4, 2011, pages 8, month 34-39.
A preparation method of a high-temperature-resistant and tough PVC cable material comprises the following steps:
the method comprises the following steps: primarily mixing PVC resin, acid-etched glass fiber, a silane coupling agent, an anti-aging agent, a composite stabilizer and a lubricant at 105 ℃ in a vacuum state, raising the temperature to 115 ℃, adding chloroprene rubber and a modified castor oil-based plasticizer for secondary mixing, and finally stirring at 1600r/min for 25min at constant temperature to obtain a mixture;
step two: and (3) placing the mixture in a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant and tough PVC cable material, wherein the extrusion conditions are as follows: the rotating speed of the screw is 600r/min, and the discharging temperature of the machine head is 170-185 ℃.
Further, in the first step, the primary mixing condition is 1100r/min for stirring for 20min, and the secondary mixing condition is 1100r/min for stirring for 10 min.
The invention has the beneficial effects that:
according to the invention, the modified castor oil-based plasticizer is introduced into the PVC base material, so that the plasticity and toughness of the PVC base material are increased, the high temperature resistance of the PVC cable material is improved, the mobility of the modified castor oil-based plasticizer is small, and the problem that the toughness of the existing PVC cable is easy to become poor after use is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the aniline derivative is prepared by the following steps:
x1, adding 0.1mol of 4-hydroxybenzaldehyde, 1% nickel acetate with the mass of 4-hydroxybenzaldehyde and 100mL of glacial acetic acid into a round-bottom flask provided with a stirrer and a thermometer, stirring and mixing uniformly, then dropwise adding 0.1mol of benzyl chloride by using a constant-pressure funnel at the dropping speed of 1 drop/second, after complete dropwise addition, carrying out reflux reaction at 130 ℃ for 3 hours, finishing the reaction, cooling to 50 ℃, carrying out reduced pressure rotary evaporation, adsorbing nickel acetate by using activated carbon, filtering, washing with water to be neutral, and drying to constant weight to obtain an intermediate 3;
x2, adding 0.1mol of intermediate 3, 0.11mol of aniline and 4mL of aniline hydrochloride into a four-neck flask with a stirrer and a nitrogen introducing device, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 2 hours, heating to 148 ℃, continuing to react at the constant temperature for 1.5 hours, cooling to 55 ℃, distilling under reduced pressure for 30 minutes after the reaction is finished, adding 2mol/L of dilute hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with 2mol/L of dilute sodium hydroxide solution until the pH value is 7, generating a precipitate, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3 times, recrystallizing a crude product twice with ethanol/water, and finally drying in vacuum at 60 ℃ for 24 hours to obtain the aniline derivative.
Example 2:
the aniline derivative is prepared by the following steps:
x1, adding 0.1mol of 4-hydroxybenzaldehyde, 3% nickel acetate with the mass of 4-hydroxybenzaldehyde and 100mL of glacial acetic acid into a round-bottom flask provided with a stirrer and a thermometer, stirring and mixing uniformly, then dropwise adding 0.1mol of benzyl chloride by using a constant-pressure funnel at the dropping speed of 2 drops/second, after the dropwise adding is completed, carrying out reflux reaction at 130 ℃ for 3 hours, finishing the reaction, cooling to 50 ℃, carrying out reduced pressure rotary evaporation, adsorbing nickel acetate by using activated carbon, filtering, washing with water to be neutral, and drying to constant weight to obtain an intermediate 3;
x2, adding 0.1mol of intermediate 3, 0.13mol of aniline and 6mL of aniline hydrochloride into a four-neck flask with a stirrer and a nitrogen introducing device, stirring uniformly, heating to 110 ℃, reacting at constant temperature for 2h, heating to 148 ℃, continuing to react at constant temperature for 1.5h, cooling to 55 ℃, distilling under reduced pressure for 30min after the reaction is finished, adding 2mol/L of dilute hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with 2mol/L of dilute sodium hydroxide solution until the pH value is 7.5, generating a precipitate, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 5 times, recrystallizing a crude product twice with ethanol/water, and finally drying in vacuum at 60 ℃ for 24h to obtain the aniline derivative.
Example 3:
the hydroxyl-containing phosphorus-nitrogen flame retardant is prepared by the following steps:
a11, uniformly mixing 0.1mol of the aniline derivative prepared in example 1, 0.25mol of triethylamine and 100mL of dried chloroform in an ice-water bath, dropwise adding 80mL of a chloroform solution containing 0.25mol of diphenyl chlorophosphate at 0 ℃, wherein the dropwise adding speed is 1 drop/second, after 5 hours of constant temperature reaction, removing the ice-water bath, raising the temperature to room temperature, continuing to react for 12 hours, then removing the solvent by vacuum distillation under reduced pressure, washing for 2 times by using 0 ℃ distilled water, finally recrystallizing by using tetrahydrofuran, and drying in vacuum to obtain an intermediate 2;
a12, adding 0.1mmol of intermediate 2 and 80mL of pyridine into a three-neck flask with a stirrer and a reflux device, introducing nitrogen for 30min, then adding 0.3g of 10% Pd/C catalyst by volume fraction, introducing hydrogen, stirring and reacting at room temperature for 24h under the protection of hydrogen, after the reaction is finished, filtering, washing with methanol for 3 times, combining the filtrates, and distilling the filtrate under reduced pressure at room temperature to obtain the hydroxyl-containing phosphorus-nitrogen flame retardant.
Example 4:
the hydroxyl-containing phosphorus-nitrogen flame retardant is prepared by the following steps:
a11, uniformly mixing 0.1mol of the aniline derivative prepared in example 1, 0.22mol of triethylamine and 100mL of dried chloroform in an ice-water bath, dropwise adding 80mL of a chloroform solution containing 0.22mol of diphenyl chlorophosphate at 0 ℃, wherein the dropwise adding speed is 1 drop/second, after 5 hours of constant temperature reaction, removing the ice-water bath, raising the temperature to room temperature, continuing to react for 12 hours, then removing the solvent by vacuum distillation under reduced pressure, washing for 2 times by using 0 ℃ distilled water, finally recrystallizing by using tetrahydrofuran, and drying in vacuum to obtain an intermediate 2;
a12, adding 0.1mmol of intermediate 2 and 30mL of pyridine into a three-neck flask with a stirrer and a reflux device, introducing nitrogen for 30min, then adding 0.1g of 10% Pd/C catalyst by volume fraction, introducing hydrogen, stirring and reacting at room temperature for 24h under the protection of hydrogen, after the reaction is finished, filtering, washing with methanol for 3 times, combining the filtrates, and distilling the filtrate under reduced pressure at room temperature to obtain the hydroxyl-containing phosphorus-nitrogen flame retardant.
Example 5:
the modified castor oil-based plasticizer is prepared by the following steps:
A. adding 0.1mol of anhydrous castor oil into a reaction kettle provided with a mechanical stirrer and a condenser, adding a mixture of 0.5% of sodium methoxide and triethanolamine by mass of the castor oil, heating to 200 ℃ under stirring, keeping the temperature and introducing nitrogen for 30min, then adding 0.15mol of glycerol, reacting for 3h at 180 ℃, cooling to room temperature, washing with water for three times, drying with anhydrous sodium sulfate, and filtering to obtain castor oil polyol;
B. adding 100g of castor oil polyol, 20g of glacial acetic acid and 1g of phosphoric acid into a round-bottom flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, uniformly mixing, dropwise adding 80g of hydrogen peroxide by using the constant-pressure dropping funnel at the dropping speed of 1 drop/second, stirring and reacting for 5 hours at 55 ℃, washing to be neutral by using distilled water, and distilling under reduced pressure at 60 ℃ to obtain epoxy castor oil;
C. mixing 0.1mol of epoxy castor oil, 0.31mol of the flame retardant containing hydroxyl phosphorus and nitrogen prepared in example 3 and 100mL of toluene, adding 0.5% potassium hydroxide flaky solid with the mass of the flame retardant containing hydroxyl phosphorus and nitrogen, reacting at 90 ℃ for 6h, washing with water to be neutral, distilling under reduced pressure, and drying in vacuum at 55 ℃ to constant weight to obtain an intermediate 1; adding 100g of the intermediate 1 and 80g of acetic anhydride into a three-neck round-bottom flask provided with a thermometer, a stirrer and a condenser, stirring and mixing uniformly, then stirring and reacting at 140 ℃ for 1.5h, cooling, washing to be neutral by using distilled water, and carrying out reduced pressure distillation at 55 ℃ to obtain the modified castor oil-based plasticizer.
Example 6:
the modified castor oil-based plasticizer is prepared by the following steps:
A. adding 0.1mol of anhydrous castor oil into a reaction kettle provided with a mechanical stirrer and a condenser, adding a mixture of 0.8% of sodium methoxide and triethanolamine, wherein the mass of the mixture is equal to that of the castor oil, stirring, heating to 200 ℃, keeping the temperature, introducing nitrogen for 30min, adding 2mol of glycerol, reacting for 3h at 200 ℃, cooling to room temperature, washing with water for three times, drying with anhydrous sodium sulfate, and filtering to obtain castor oil polyol;
B. adding 100g of castor oil polyol, 50g of glacial acetic acid and 2g of phosphoric acid into a round-bottom flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, uniformly mixing, dropwise adding 100g of hydrogen peroxide into the constant-pressure dropping funnel at the dropping speed of 2 drops/second, stirring and reacting for 5 hours at 55 ℃, washing to be neutral by using distilled water, and distilling at 60 ℃ under reduced pressure to obtain epoxy castor oil;
C. mixing 0.1mol of epoxy castor oil, 0.32mol of the flame retardant containing hydroxyl phosphorus and nitrogen prepared in example 3 and 100mL of toluene, adding 1.5% potassium hydroxide flaky solid with the mass of the flame retardant containing hydroxyl phosphorus and nitrogen, reacting at 90 ℃ for 6h, washing with water to be neutral, distilling under reduced pressure, and drying in vacuum at 55 ℃ to constant weight to obtain an intermediate 1; adding 100g of the intermediate 1 and 100g of acetic anhydride into a three-neck round-bottom flask provided with a thermometer, a stirrer and a condenser, stirring and mixing uniformly, then stirring and reacting at 140 ℃ for 1.5h, cooling, washing to be neutral by using distilled water, and carrying out reduced pressure distillation at 55 ℃ to obtain the modified castor oil-based plasticizer.
Example 7:
a high-temperature-resistant and tough PVC cable material comprises the following raw materials in parts by weight: 90 parts of PVC resin, 14 parts of chloroprene rubber, 8 parts of modified castor oil-based plasticizer, 2.5 parts of acid-etched glass fiber, 1 part of silane coupling agent, 1.5 parts of anti-aging agent, 2 parts of composite stabilizer and 1.5 parts of lubricant, wherein the lubricant is magnesium stearate, calcium stearate and zinc stearate, and the mass ratio of the lubricant to the lubricant is 1: 1: 1, mixing to form a mixture; the anti-aging agent is an ultraviolet absorbent UV-329 and an antioxidant CA according to the mass ratio of 1: 2, mixing to form the composition; the composite stabilizer is a calcium/zinc composite stabilizer.
The PVC cable material is prepared by the following steps:
the method comprises the following steps: primarily mixing PVC resin, acid-etched glass fiber, a silane coupling agent, an anti-aging agent, a composite stabilizer and a lubricant at 105 ℃ under a vacuum state, raising the temperature to 115 ℃, adding chloroprene rubber and a modified castor oil-based plasticizer for secondary mixing, and finally stirring for 25min at 1600r/min at constant temperature to obtain a mixture, wherein the primary mixing condition is that stirring is performed at 1100r/min for 20min, and the secondary mixing condition is that stirring is performed at 1100r/min for 10 min;
step two: and (3) placing the mixture in a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant and tough PVC cable material, wherein the extrusion conditions are as follows: the rotating speed of the screw is 600r/min, and the discharging temperature of the machine head is 170 ℃.
Example 8:
a high-temperature-resistant and tough PVC cable material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 18 parts of chloroprene rubber, 11 parts of modified castor oil-based plasticizer, 4 parts of acid-etched glass fiber, 1.5 parts of silane coupling agent, 3 parts of anti-aging agent, 3 parts of composite stabilizer and 2 parts of lubricant, wherein the lubricant is magnesium stearate, calcium stearate and zinc stearate, and the mass ratio of the lubricant to the lubricant is 1: 1: 1, mixing to form; the anti-aging agent is an ultraviolet absorbent UV-329 and an antioxidant CA according to the mass ratio of 1: 2, mixing to form the composition; the composite stabilizer is a calcium/zinc composite stabilizer.
The PVC cable material is prepared by the following steps:
the method comprises the following steps: firstly mixing PVC resin, acid-etched glass fiber, a silane coupling agent, an anti-aging agent, a composite stabilizer and a lubricant at 105 ℃ in a vacuum state, raising the temperature to 115 ℃, adding chloroprene rubber and a modified castor oil-based plasticizer for secondary mixing, and finally stirring at 1600r/min for 25min at constant temperature to obtain a mixture, wherein the primary mixing condition is that stirring is carried out at 1100r/min for 20min, and the secondary mixing condition is that stirring is carried out at 1100r/min for 10 min;
step two: and (3) placing the mixture in a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant and tough PVC cable material, wherein the extrusion conditions are as follows: the screw rotation speed is 600r/min, and the head discharge temperature is 175 ℃.
Example 9:
a high-temperature-resistant and tough PVC cable material comprises the following raw materials in parts by weight: 120 parts of PVC resin, 22 parts of chloroprene rubber, 15 parts of modified castor oil based plasticizer, 6.5 parts of acid etched glass fiber, 2 parts of silane coupling agent, 5.5 parts of anti-aging agent, 4 parts of composite stabilizer and 3 parts of lubricant, wherein the lubricant is magnesium stearate, calcium stearate and zinc stearate according to the mass ratio of 1: 1: 1, mixing to form a mixture; the anti-aging agent is an ultraviolet absorbent UV-329 and an antioxidant CA according to the mass ratio of 1: 2, mixing to form the composition; the composite stabilizer is a calcium/zinc composite stabilizer.
The PVC cable material is prepared by the following steps:
the method comprises the following steps: primarily mixing PVC resin, acid-etched glass fiber, a silane coupling agent, an anti-aging agent, a composite stabilizer and a lubricant at 105 ℃ under a vacuum state, raising the temperature to 115 ℃, adding chloroprene rubber and a modified castor oil-based plasticizer for secondary mixing, and finally stirring for 25min at 1600r/min at constant temperature to obtain a mixture, wherein the primary mixing condition is that stirring is performed at 1100r/min for 20min, and the secondary mixing condition is that stirring is performed at 1100r/min for 10 min;
step two: and (3) placing the mixture in a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant and tough PVC cable material, wherein the extrusion conditions are as follows: the rotating speed of the screw is 600r/min, and the discharging temperature of the machine head is 185 ℃.
Comparative example 1:
the phosphorus-nitrogen flame retardant is prepared by the following steps:
0.1mol of p-phenylenediamine, 0.22mol of triethylamine and 100mL of dried chloroform are uniformly mixed in an ice-water bath, 80mL of chloroform solution containing 0.22mol of diphenyl chlorophosphate is dropwise added at 0 ℃, the dropping speed is 1 drop/second, after 5 hours of constant temperature reaction, the ice-water bath is removed, the temperature is raised to room temperature for further reaction for 12 hours, then the solvent is removed by vacuum distillation under reduced pressure, the mixture is washed for 2 times by 0 ℃ distilled water, finally, the mixture is recrystallized by tetrahydrofuran and dried in vacuum, and the phosphorus-nitrogen flame retardant is obtained.
Comparative example 2:
the modified castor oil-based plasticizer is prepared by the following steps:
A. adding 0.1mol of anhydrous castor oil into a reaction kettle provided with a mechanical stirrer and a condenser, adding a mixture of 0.5% of sodium methoxide and triethanolamine, wherein the mass of the mixture is equal to that of the castor oil, heating to 200 ℃ while stirring, keeping the temperature, introducing nitrogen for 30min, then adding 0.15mol of glycerol, reacting for 3h at 180 ℃, cooling to room temperature, washing with water for three times, drying with anhydrous sodium sulfate, and filtering to obtain castor oil polyol;
B. adding 100g of castor oil polyol, 20g of glacial acetic acid and 1g of phosphoric acid into a round-bottom flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, uniformly mixing, dropwise adding 80g of hydrogen peroxide by using the constant-pressure dropping funnel at the dropping speed of 1 drop/second, stirring and reacting for 5 hours at 55 ℃, washing to be neutral by using distilled water, and distilling under reduced pressure at 60 ℃ to obtain epoxy castor oil;
C. mixing 0.1mol of epoxy castor oil, 0.31mol of phosphorus-nitrogen flame retardant prepared in comparative example 1 and 100mL of toluene, adding 0.5% sodium hydroxide flaky solid with the mass of hydroxyl-containing phosphorus-nitrogen flame retardant, reacting at 90 ℃ for 6h, washing with water to be neutral, distilling under reduced pressure, and drying in vacuum at 55 ℃ to constant weight to obtain an intermediate 1; adding 100g of the intermediate 1 and 80g of acetic anhydride into a three-neck round-bottom flask provided with a thermometer, a stirrer and a condenser, stirring and mixing uniformly, then stirring and reacting at 140 ℃ for 1.5h, cooling, washing to be neutral by using distilled water, and carrying out reduced pressure distillation at 55 ℃ to obtain the modified castor oil-based plasticizer.
Comparative example 3:
the modified castor oil-based plasticizer is prepared by the following steps:
A. adding 0.1mol of anhydrous castor oil into a reaction kettle provided with a mechanical stirrer and a condenser, adding a mixture of 0.8% of sodium methoxide and triethanolamine, wherein the mass of the mixture is equal to that of the castor oil, stirring, heating to 200 ℃, keeping the temperature, introducing nitrogen for 30min, adding 2mol of glycerol, reacting for 3h at 200 ℃, cooling to room temperature, washing with water for three times, drying with anhydrous sodium sulfate, and filtering to obtain castor oil polyol;
B. adding 100g of castor oil polyol, 50g of glacial acetic acid and 2g of phosphoric acid into a round-bottom flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, uniformly mixing, dropwise adding 100g of hydrogen peroxide into the constant-pressure dropping funnel at the dropping speed of 2 drops/second, stirring and reacting for 5 hours at 55 ℃, washing to be neutral by using distilled water, and distilling at 60 ℃ under reduced pressure to obtain epoxy castor oil;
C. mixing 0.1mol of epoxy castor oil, 0.32mol of DOPO flame retardant and 100mL of toluene, reacting at 160 ℃ for 6h, washing to be neutral, distilling under reduced pressure, and drying at 55 ℃ in vacuum to constant weight to obtain an intermediate 1; adding 100g of the intermediate 1 and 80g of acetic anhydride into a three-neck round-bottom flask provided with a thermometer, a stirrer and a condenser, stirring and mixing uniformly, then stirring and reacting at 140 ℃ for 1.5h, cooling, washing to be neutral by using distilled water, and carrying out reduced pressure distillation at 55 ℃ to obtain the modified castor oil-based plasticizer.
Comparative example 4:
a high-temperature-resistant and tough PVC cable material comprises the following raw materials in parts by weight: 90 parts of PVC resin, 14 parts of chloroprene rubber, 8 parts of modified castor oil-based plasticizer prepared in comparative example 2, 2.5 parts of acid-etched glass fiber, 1 part of silane coupling agent, 1.5 parts of anti-aging agent, 2 parts of composite stabilizer and 1.5 parts of lubricant, wherein the lubricant is magnesium stearate, calcium stearate and zinc stearate, and the mass ratio of the lubricant to the lubricant is 1: 1: 1, mixing to form a mixture; the anti-aging agent is an ultraviolet absorbent UV-329 and an antioxidant CA according to the mass ratio of 1: 2, mixing to form; the composite stabilizer is a calcium/zinc composite stabilizer.
The PVC cable material is prepared by the following steps: the procedure is as in example 7.
Comparative example 5:
a high-temperature-resistant flexible PVC cable material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 18 parts of chloroprene rubber, 11 parts of modified castor oil-based plasticizer prepared in comparative example 3, 4 parts of acid-etched glass fiber, 1.5 parts of silane coupling agent, 3 parts of anti-aging agent, 3 parts of composite stabilizer and 2 parts of lubricant, wherein the lubricant is magnesium stearate, calcium stearate and zinc stearate according to the mass ratio of 1: 1: 1, mixing to form a mixture; the anti-aging agent is an ultraviolet absorbent UV-329 and an antioxidant CA according to the mass ratio of 1: 2, mixing to form the composition; the composite stabilizer is a calcium/zinc composite stabilizer.
The PVC cable material is prepared by the following steps: the procedure is as in example 8.
Comparative example 6:
a high-temperature-resistant and tough PVC cable material comprises the following raw materials in parts by weight: 120 parts of PVC resin, 22 parts of chloroprene rubber, 15 parts of diisodecyl phthalate, 2 parts of DOPO flame retardant, 6.5 parts of acid-etched glass fiber, 2 parts of silane coupling agent, 5.5 parts of anti-aging agent, 4 parts of composite stabilizer and 3 parts of lubricant, wherein the lubricant is magnesium stearate, calcium stearate and zinc stearate, and the mass ratio of the lubricant to the lubricant is 1: 1: 1, mixing to form a mixture; the anti-aging agent is an ultraviolet absorbent UV-329 and an antioxidant CA according to the mass ratio of 1: 2, mixing to form; the composite stabilizer is a calcium/zinc composite stabilizer.
The PVC cable material is prepared by the following steps: the same procedure was used to prepare example 9.
Example 10:
the PVC cable materials prepared in examples 7 to 9 and comparative examples 4 to 6 were subjected to the following performance tests:
tensile strength, elongation at break: testing according to GB/T2951;
limiting oxygen index: testing according to ISO 4586;
resistance to extraction: cutting a PVC cable into 2cm sections, respectively placing the PVC cable into a solvent such as distilled water, a 3% acetic acid solution, a 10% ethanol solution, petroleum ether, olive oil and the like, keeping the PVC cable for 24 hours in an environment with the relative humidity of (25 +/-2) DEG C and (50 +/-5)% and taking out the PVC cable to be wiped clean by using parchment paper, keeping the PVC cable for 24 hours in an oven with the temperature of 30 ℃, and weighing the weight of the PVC cable material. The mass loss rate of the plasticizer was calculated using the following formula: the mass loss rate is [ (m1-m2)/m1) ] x 100, wherein m1 is the original mass of the PVC cable, and m2 is the mass of the PVC cable after the test;
stabilization time at 200 ℃: testing with TG: in nitrogen atmosphere, the heating rate is 10 ℃/min, and the temperature is between room temperature and 650 ℃.
The results of the above tests are shown in the following table.
As can be seen from the data of tensile strength and elongation at break, the PVC cable material provided by the invention has good toughness, the limited oxygen index data shows that the PVC cable material provided by the invention has good flame retardant property, the data of the stabilization time at 200 ℃ shows that the thermal stability of the PVC cable material obtained in examples 7-9 is better than that of the PVC cable material obtained in comparative examples 4-6, and the data of the drawing resistance shows that the drawing resistance of the PVC cable material obtained in examples 7-9 is better than that of the PVC cable material obtained in comparative examples 4-6, which indicates that the modified castor oil-based plasticizer added in the PVC cable material provided by the invention has small migration.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. The high-temperature-resistant and tough PVC cable material is characterized in that: the method comprises the following raw materials: PVC resin, chloroprene rubber, a modified castor oil based plasticizer, acid etched glass fiber, a silane coupling agent, an anti-aging agent, a composite stabilizer and a lubricant;
the modified castor oil-based plasticizer is prepared by the following steps:
mixing epoxy castor oil, a hydroxyl-containing phosphorus-nitrogen flame retardant and toluene, adding a potassium hydroxide flaky solid, reacting at 90 ℃ for 6 hours, washing with water to be neutral, distilling under reduced pressure, and drying in vacuum to obtain an intermediate 1; uniformly mixing the intermediate 1 and acetic anhydride, stirring at 140 ℃ for reaction for 1.5h, washing to be neutral, and distilling under reduced pressure to obtain a modified castor oil-based plasticizer;
the hydroxyl-containing phosphorus-nitrogen flame retardant is prepared by the following steps:
a11, uniformly mixing aniline derivatives, triethylamine and dry chloroform, dropwise adding a chloroform solution of diphenyl chlorophosphate at 0 ℃, reacting for 5 hours, heating to room temperature, continuing to react for 12 hours, then carrying out reduced pressure distillation under vacuum, washing with water, recrystallizing, and drying under vacuum to obtain an intermediate 2;
a12, mixing the intermediate 2 with pyridine, introducing nitrogen for 30min, adding a Pd/C catalyst with the volume fraction of 10%, stirring and reacting at room temperature for 24h under the protection of hydrogen, and performing aftertreatment to obtain the hydroxyl-containing phosphorus-nitrogen flame retardant;
the aniline derivative is prepared by the following steps:
x1, uniformly mixing 4-hydroxybenzaldehyde, nickel acetate and glacial acetic acid, dropwise adding benzyl chloride, after completely dropwise adding, carrying out reflux reaction at 130 ℃ for 3 hours, then carrying out reduced pressure rotary evaporation, filtering, washing with water, and drying to obtain an intermediate 3;
and X2, uniformly stirring the intermediate 3, aniline and aniline hydrochloride, heating to 110 ℃, reacting for 2 hours, heating to 148 ℃, continuing to react for 1.5 hours, and performing post-treatment to obtain the aniline derivative.
2. The high-temperature-resistant flexible PVC cable material according to claim 1, characterized in that: the PVC cable material comprises the following raw materials in parts by weight: 90-120 parts of PVC resin, 14-22 parts of chloroprene rubber, 8-15 parts of modified castor oil based plasticizer, 2.5-6.5 parts of acid etched glass fiber, 1-2 parts of silane coupling agent, 1.5-5.5 parts of anti-aging agent, 2-4 parts of composite stabilizer and 1.5-3 parts of lubricant.
3. The high-temperature-resistant flexible PVC cable material according to claim 1, characterized in that: the epoxy castor oil is prepared by the following steps:
A. uniformly mixing anhydrous castor oil, sodium methoxide and triethanolamine, heating to 200 ℃, introducing nitrogen for 30min, then adding glycerol, reacting for 3h at the temperature of 180-200 ℃, cooling to room temperature, washing with water, drying, and filtering to obtain castor oil polyol;
B. uniformly mixing castor oil polyalcohol, glacial acetic acid and phosphoric acid, dropwise adding hydrogen peroxide, stirring and reacting at 55 ℃ for 5 hours after dropwise adding, washing with water to neutrality, and distilling under reduced pressure to obtain the epoxy castor oil.
4. The preparation method of the high temperature resistant flexible PVC cable material according to claim 1, characterized in that: the method comprises the following steps:
the method comprises the following steps: firstly mixing PVC resin, acid-etched glass fiber, a silane coupling agent, an anti-aging agent, a composite stabilizer and a lubricant at 105 ℃ under vacuum, raising the temperature to 115 ℃, adding chloroprene rubber and a modified castor oil-based plasticizer for secondary mixing, and finally stirring at 1600r/min for 25min at constant temperature to obtain a mixture;
step two: and extruding the mixture by a double-screw extruder, and granulating to obtain the high-temperature-resistant and tough PVC cable material.
5. The preparation method of the high temperature resistant flexible PVC cable material according to claim 4, characterized in that: in the first step, the primary mixing condition is that the mixture is stirred for 20min at 1100r/min, and the secondary mixing condition is that the mixture is stirred for 10min at 1100 r/min.
6. The preparation method of the high temperature resistant flexible PVC cable material according to claim 4, characterized in that: the extrusion conditions in the second step are as follows: the rotating speed of the screw is 600r/min, and the discharging temperature of the machine head is 170-185 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110975285.0A CN113652039B (en) | 2021-08-24 | 2021-08-24 | High-temperature-resistant and tough PVC cable material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110975285.0A CN113652039B (en) | 2021-08-24 | 2021-08-24 | High-temperature-resistant and tough PVC cable material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113652039A CN113652039A (en) | 2021-11-16 |
| CN113652039B true CN113652039B (en) | 2022-09-06 |
Family
ID=78481830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110975285.0A Active CN113652039B (en) | 2021-08-24 | 2021-08-24 | High-temperature-resistant and tough PVC cable material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113652039B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736471A (en) * | 2022-04-11 | 2022-07-12 | 界首市锦丰塑业有限公司 | Production process of toughened waste polyvinyl chloride |
| CN114783675B (en) * | 2022-05-27 | 2023-08-18 | 广东南洋电缆股份有限公司 | Multi-layer composite isolation type flexible mineral fireproof cable and preparation method thereof |
| CN114920882B (en) * | 2022-07-06 | 2023-11-07 | 宁夏永大石化有限公司 | Polypropylene material with high thermal stability |
| CN117777618A (en) * | 2023-12-27 | 2024-03-29 | 苏州亨利通信材料有限公司 | Environment-friendly ultraviolet-resistant PVC cable sheath material and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594286A (en) * | 1985-05-07 | 1986-06-10 | Graniteville Company | Coated fabric |
| CN1113922C (en) * | 1997-05-28 | 2003-07-09 | 三井化学株式会社 | Polyoxyalkylenepolyols, derivatives thereof, and process for producing polyoxyalkylenepolyols |
| JP4450906B2 (en) * | 1999-11-09 | 2010-04-14 | 日鉄防蝕株式会社 | Polyurethane composition for cast coating of steel |
| JP2006335874A (en) * | 2005-06-02 | 2006-12-14 | Kao Corp | Plasticizer for biodegradable resin |
| CN102272215A (en) * | 2008-12-18 | 2011-12-07 | 埃克森美孚化学专利公司 | Godwin allen d [us]; gosse claudius [be] |
| SG10201508216WA (en) * | 2011-10-14 | 2015-11-27 | Galata Chemicals Llc | Plasticizers derived from renewable feedstock |
| JP6159741B2 (en) * | 2013-01-30 | 2017-07-05 | アルヴィンド マリナース ラリ、 | Enzymatic methods for the hydrolysis of lipids and oily substances |
| CN103319675B (en) * | 2013-05-24 | 2015-07-29 | 中国林业科学研究院林产化学工业研究所 | Castor oil-base flame-proof polyol composition and method of making the same and application |
| CN105218781A (en) * | 2015-09-15 | 2016-01-06 | 江苏锦宇环境工程有限公司 | A kind of preparation method of urethane foam insulation fire retardant material |
| CA3011348A1 (en) * | 2016-01-13 | 2017-07-20 | Arkema Inc. | Methods of producing epoxidized fatty acid alkyl esters useful as plasticizers |
-
2021
- 2021-08-24 CN CN202110975285.0A patent/CN113652039B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113652039A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113652039B (en) | High-temperature-resistant and tough PVC cable material and preparation method thereof | |
| CN115403846B (en) | Nano-material HDPE (high-density polyethylene) pipe and production method thereof | |
| CN113956777B (en) | Preparation and application methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating | |
| CN109912804B (en) | Preparation method of phosphorus-nitrogen modified lignin-based intumescent flame retardant | |
| CN109369958B (en) | Preparation method and application of organically modified zirconium phosphate | |
| CN113999499A (en) | Flame-retardant reinforced regenerated PET composite material | |
| CN114891451A (en) | Compound thermoplastic polymer TPO waterproofing membrane | |
| CN117070180B (en) | Reactive polyurethane hot melt adhesive and preparation method thereof | |
| CN112442073A (en) | Phosphorus-containing reactive flame retardant and preparation method and application thereof | |
| CN113429703A (en) | PVC polymer composite flame-retardant waterproof coiled material | |
| CN115850641B (en) | Flame-retardant modified polyurethane material and synthesis method thereof | |
| CN110423443B (en) | Biomass-based high-toughness flame-retardant plate | |
| CN116478461A (en) | Rubber sealing material and preparation method thereof | |
| CN115073861A (en) | Anti-tensile polyvinyl chloride communication pipe and preparation method thereof | |
| CN112430325B (en) | Synthesis method of inert end group polythioether polymer | |
| CN114957969A (en) | Acetylated lignin modification-based polyurethane oil absorption foam and preparation method and application thereof | |
| CN116218195B (en) | High-flame-retardance modified polyurethane cable material and preparation method thereof | |
| CN117363031B (en) | Phosphorus-containing flame-retardant master batch and preparation method thereof | |
| CN113136055A (en) | Packaging material based on biodegradation technology | |
| CN112480305A (en) | Adamantyl phenyl sulfonate based polymeric flame retardant, preparation method and application | |
| CN117089153B (en) | Environment-friendly modified PVC material | |
| CN116948480B (en) | Heat-resistant aqueous acrylic ester emulsion and preparation method thereof | |
| CN114775084B (en) | Large-disc-diameter flame-retardant polypropylene filling rope | |
| CN115124811B (en) | Composite board for subway tunnel evacuation platform | |
| CN109825075B (en) | Halogen-free flame-retardant thermoplastic elastomer cable material for new energy automobile |
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 |