CN114213787A - Preparation method of high-strength hard polyvinyl chloride colloidal particles - Google Patents
Preparation method of high-strength hard polyvinyl chloride colloidal particles Download PDFInfo
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- CN114213787A CN114213787A CN202210084946.5A CN202210084946A CN114213787A CN 114213787 A CN114213787 A CN 114213787A CN 202210084946 A CN202210084946 A CN 202210084946A CN 114213787 A CN114213787 A CN 114213787A
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- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 113
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 113
- 239000002245 particle Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000010306 acid treatment Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- -1 chlorine radicals Chemical class 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the technical field of polyvinyl chloride, and particularly relates to a preparation method of high-strength hard polyvinyl chloride colloidal particles, which comprises the steps of carrying out alkali treatment and acid treatment on cage-type polysilsesquioxane dispersion liquid, and carrying out chlorination drying to obtain chlorinated cage-type polysilsesquioxane; adding polyvinyl chloride into a reaction kettle, and adding cyclohexanone to dissolve the polyvinyl chloride to obtain polyvinyl chloride slurry; adding chlorinated cage type polysilsesquioxane into polyvinyl chloride slurry, and uniformly stirring to obtain a mixture; extruding and granulating the mixture by using an extruder to obtain prefabricated PVC colloidal particles; s5, placing the prefabricated PVC colloidal particles into a reaction kettle, standing for 2-5h at a constant temperature, taking out the colloidal particles, and drying to obtain the high-strength rigid polyvinyl chloride colloidal particles. According to the invention, the surface functional group type connection is formed by the surface functional group of the cage type polysilsesquioxane and the polyvinyl chloride, so that the corresponding performance of the polyvinyl chloride is maintained, the mechanical performance of the polyvinyl chloride is enhanced according to the cage type polysilsesquioxane, and the weather resistance influence is not caused.
Description
Technical Field
The invention belongs to the technical field of polyvinyl chloride, and particularly relates to a preparation method of high-strength hard polyvinyl chloride colloidal particles.
Background
The PVC resin is used as general plastic, and is widely applied to the fields of various food packages, medical packages, cosmetic packages, household appliance packages, electronic and electrical packages, automobile accessories, chemical materials, building decoration and building materials, fire-fighting equipment accessories, sanitary wares, retail supermarket shelves, water treatment environment-friendly pipes, pipe fittings and the like due to the relatively low price and the modified easy processability. The polyvinyl chloride has excellent flame retardant property, wear resistance, corrosion resistance, dielectric property and sealing property due to the special molecular structure of the polyvinyl chloride. However, in the anti-process of polyvinyl chloride, the impact resistance and the temperature resistance are poor, so that the application field of the polyvinyl chloride is limited. The existing polyvinyl chloride process uses a high molecular elastomer as an impact modifier, and although the impact resistance effect can be improved, the added elastomer can cause the weather resistance to be reduced, and the practicability of the polyvinyl chloride cannot be improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the preparation method of the high-strength hard polyvinyl chloride colloidal particles, which utilizes the surface functional group of the cage-type polysilsesquioxane to form surface functional group type connection with the polyvinyl chloride, not only maintains the corresponding performance of the polyvinyl chloride, but also enhances the mechanical performance of the polyvinyl chloride according to the cage-type polysilsesquioxane, and cannot cause weather resistance influence.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the preparation method of the high-strength rigid polyvinyl chloride colloidal particles comprises the following steps:
s1, performing alkali treatment and acid treatment on the cage-type polysilsesquioxane dispersion liquid, and chloridizing and drying to obtain chlorinated cage-type polysilsesquioxane;
s2, adding polyvinyl chloride into the reaction kettle, and adding cyclohexanone to dissolve the polyvinyl chloride to obtain polyvinyl chloride slurry;
s3, adding the chlorinated cage-type polysilsesquioxane obtained in the step S1 into the polyvinyl chloride slurry obtained in the step 2, and uniformly stirring to obtain a mixture;
s4, extruding and granulating the mixture obtained in the step S3 by using an extruder to obtain prefabricated PVC rubber particles;
s5, placing the prefabricated PVC colloidal particles into a reaction kettle, standing for 2-5h at a constant temperature, taking out the colloidal particles, and drying to obtain the high-strength rigid polyvinyl chloride colloidal particles.
In certain embodiments, in step S1, subjecting the cage polysilsesquioxane to ultrasound to obtain a cage polysilsesquioxane dispersion having a concentration of 30-50 g/L; the cage-type polysilsesquioxane adopts polyfunctional cage-type polysilsesquioxane, and all R groups are reactive groups.
In some embodiments, in step S1, the alkali treatment is ultrasonic treatment with 0.01-0.04mol/L sodium hydroxide solution for 10-60min, stirring and water washing to neutral and drying, and the ultrasonic treatment frequency is 50-80kHz and the temperature is 50-70 ℃; the acid treatment is to treat for 20-60min by using 0.1-0.5mol/L hydrochloric acid, stir at constant temperature and wash with water; and the stirring temperature at constant temperature is 30-60 ℃.
In some embodiments, in step S1, the chlorination is performed by reflux reaction of thionyl chloride and chloroform at a reflux temperature of 70-75 ℃, a mass ratio of the thionyl chloride to the cage-type polysilsesquioxane is 1:3-4, and a volume ratio of the chloroform to the thionyl chloride is 4-6: 1.
In some embodiments, in step S2, the polyvinyl chloride in the polyvinyl chloride slurry is 20 to 50% by mass.
In certain embodiments, in step S3, the mass of the chlorinated cage polysilsesquioxane in the mixture is 10-30% of the mass of the polyvinyl chloride.
In certain embodiments, the extruder temperature is 170-190 ℃ in step S4.
In some embodiments, in step S5, the reaction kettle is filled with nitrogen and water vapor, and the volume ratio of the nitrogen to the water vapor is 14-20: 1.
In certain embodiments, in step 5, the temperature of the constant temperature standing is 80-90 ℃.
In some embodiments, in step 5, the temperature for drying is 110-.
From the above description, it can be seen that the present invention has the following advantages:
according to the high-strength hard polyvinyl chloride sizing material, the Si-O alternate connection structure in the self structure of the cage-type polysilsesquioxane is utilized, the mechanical property of polyvinyl chloride is effectively improved, the impact resistance is greatly improved, meanwhile, the chemical activity of the surface of the cage-type polysilsesquioxane can promote the cage-type polysilsesquioxane to form strong chemical bond combination with polyvinyl chloride in the extrusion process, and the problems of inorganic particle agglomeration and weak two-phase interface binding force do not exist; in the whole process, the extruded rubber material has an internal permeation effect in a water vapor environment, and hydrolysis reaction is formed in the cage-type polysilsesquioxane. Furthermore, the strong chemical activity on the surface of the cage-type polysilsesquioxane can effectively prevent the polyvinyl chloride from being oxidized, and when active chlorine radicals are formed, the surface of the cage-type polysilsesquioxane can attract the chlorine radicals to achieve the effect of fixing the chlorine radicals, so that the damage to the polyvinyl chloride structure is effectively reduced, and therefore, the weather resistance can be improved by adding the cage-type polysilsesquioxane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below.
Example 1
The preparation method of the high-strength rigid polyvinyl chloride colloidal particles provided by the embodiment has the following specific technical scheme:
the preparation method of the high-strength rigid polyvinyl chloride colloidal particles comprises the following steps:
1. preparation of chlorinated cage polysilsesquioxane:
selecting cage type polysilsesquioxane of which all R groups are reactive groups as a raw material, namely cage type polysilsesquioxane, and carrying out ultrasonic treatment on the cage type polysilsesquioxane to obtain cage type polysilsesquioxane dispersion liquid with the concentration of 30 g/L; performing ultrasonic treatment for 10min by using 0.01mol/L sodium hydroxide solution, stirring, washing with water to neutrality, and drying at 50kHz and 50 ℃ under ultrasonic treatment; then, treating for 20min by using 0.1mol/L hydrochloric acid, stirring at constant temperature and washing with water; and stirring at the constant temperature of 30 ℃, performing reflux reaction on thionyl chloride and chloroform at the reflux temperature of 70 ℃, wherein the mass ratio of the thionyl chloride to the cage-type polysilsesquioxane is 1:3, and the volume ratio of the chloroform to the thionyl chloride is 4:1, and drying to obtain the chlorinated cage-type polysilsesquioxane.
2. Preparation of polyvinyl chloride slurry
Directly putting PVC colloidal particles into a reaction kettle, adding cyclohexanone, and dissolving PVC overnight to obtain PVC slurry; wherein the mass ratio of the polyvinyl chloride is 20%.
3. Preparation of the mixture
Adding chlorinated cage type polysilsesquioxane into polyvinyl chloride slurry, and uniformly stirring to obtain a mixture, wherein the mass of the chlorinated cage type polysilsesquioxane is 10% of that of the polyvinyl chloride.
4. Preparation of prefabricated PVC colloidal particles
And (3) putting the PVC modified material into an extruder, and extruding and granulating at 170 ℃.
5. Preparation of high-strength hard polyvinyl chloride colloidal particles
Placing the prefabricated PVC colloidal particles into a reaction kettle, standing for 2 hours at a constant temperature, taking out the colloidal particles, and drying to obtain high-strength hard polyvinyl chloride colloidal particles; wherein the reaction kettle is filled with nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 14:1, the temperature of constant temperature standing is 80 ℃, and the temperature of drying is 110 ℃.
Through detection, the Vicat softening temperature of the high-strength rigid polyvinyl chloride colloidal particles of the embodiment is 75 ℃, the impact strength reaches 150J/m, and the tensile strength before illumination is 491Kg/m2The tensile strength after 1000 hours of illumination was 405Kg/m2。
Example 2
The preparation method of the high-strength rigid polyvinyl chloride colloidal particles provided by the embodiment has the following specific technical scheme:
the preparation method of the high-strength rigid polyvinyl chloride colloidal particles comprises the following steps:
1. preparation of chlorinated cage polysilsesquioxane:
selecting cage type polysilsesquioxane of which all R groups are reactive groups as a raw material, namely cage type polysilsesquioxane, and carrying out ultrasonic treatment on the cage type polysilsesquioxane to obtain cage type polysilsesquioxane dispersion liquid with the concentration of 50 g/L; carrying out ultrasonic treatment for 60min by using 0.04mol/L sodium hydroxide solution, stirring, washing with water to be neutral, and drying, wherein the ultrasonic treatment frequency is 80kHz, and the temperature is 70 ℃; then, treating for 60min by using 0.5mol/L hydrochloric acid, stirring at constant temperature and washing; and stirring at the constant temperature of 60 ℃, performing reflux reaction on thionyl chloride and chloroform at the reflux temperature of 75 ℃, wherein the mass ratio of the thionyl chloride to the cage-type polysilsesquioxane is 1:4 and the volume ratio of the chloroform to the thionyl chloride is 6:1, and drying to obtain the chlorinated cage-type polysilsesquioxane.
2. Preparation of polyvinyl chloride slurry
Directly putting PVC colloidal particles into a reaction kettle, adding cyclohexanone, and dissolving PVC overnight to obtain PVC slurry; wherein the mass ratio of the polyvinyl chloride is 50%.
3. Preparation of the mixture
Adding chlorinated cage type polysilsesquioxane into polyvinyl chloride slurry, and uniformly stirring to obtain a mixture, wherein the mass of the chlorinated cage type polysilsesquioxane is 30% of that of the polyvinyl chloride.
4. Preparation of prefabricated PVC colloidal particles
And (3) putting the PVC modified material into an extruder, and extruding and granulating at 190 ℃.
5. Preparation of high-strength hard polyvinyl chloride colloidal particles
Placing the prefabricated PVC colloidal particles into a reaction kettle, standing for 5 hours at a constant temperature, taking out the colloidal particles, and drying to obtain high-strength hard polyvinyl chloride colloidal particles; wherein the reaction kettle is filled with nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 20:1, the temperature of constant temperature standing is 90 ℃, and the temperature of drying is 130 ℃.
Through detection, the Vicat softening temperature of the high-strength rigid polyvinyl chloride colloidal particles of the embodiment is 79 ℃, the impact strength reaches 150J/m, and the tensile strength before illumination is 501Kg/m2The tensile strength after 1000 hours of illumination is 421Kg/m2。
Example 3
The preparation method of the high-strength rigid polyvinyl chloride colloidal particles provided by the embodiment has the following specific technical scheme:
the preparation method of the high-strength rigid polyvinyl chloride colloidal particles comprises the following steps:
1. preparation of chlorinated cage polysilsesquioxane:
selecting cage type polysilsesquioxane of which all R groups are reactive groups as a raw material, namely cage type polysilsesquioxane, and carrying out ultrasonic treatment on the cage type polysilsesquioxane to obtain cage type polysilsesquioxane dispersion liquid with the concentration of 40 g/L; carrying out ultrasonic treatment for 30min by using 0.03mol/L sodium hydroxide solution, stirring, washing to be neutral, and drying, wherein the ultrasonic treatment frequency is 70kHz, and the temperature is 60 ℃; then, treating for 40min by using 0.3mol/L hydrochloric acid, stirring at constant temperature and washing with water; and stirring at the constant temperature of 50 ℃, performing reflux reaction on thionyl chloride and chloroform at the reflux temperature of 73 ℃, wherein the mass ratio of the thionyl chloride to the cage-type polysilsesquioxane is 1:4, and the volume ratio of the chloroform to the thionyl chloride is 5:1, and drying to obtain the chlorinated cage-type polysilsesquioxane.
2. Preparation of polyvinyl chloride slurry
Directly putting PVC colloidal particles into a reaction kettle, adding cyclohexanone, and dissolving PVC overnight to obtain PVC slurry; wherein the mass percentage of the polyvinyl chloride is 20-50%.
3. Preparation of the mixture
Adding chlorinated cage type polysilsesquioxane into polyvinyl chloride slurry, and uniformly stirring to obtain a mixture, wherein the mass of the chlorinated cage type polysilsesquioxane is 20% of that of the polyvinyl chloride.
4. Preparation of prefabricated PVC colloidal particles
And (3) putting the PVC modified material into an extruder, and extruding and granulating at 180 ℃.
5. Preparation of high-strength hard polyvinyl chloride colloidal particles
Placing the prefabricated PVC colloidal particles into a reaction kettle, standing for 4 hours at a constant temperature, taking out the colloidal particles, and drying to obtain high-strength hard polyvinyl chloride colloidal particles; wherein the reaction kettle is filled with nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 18:1, the temperature of constant temperature standing is 85 ℃, and the temperature of drying is 120 ℃.
Through detection, the Vicat softening temperature of the high-strength rigid polyvinyl chloride colloidal particles of the embodiment is 78 ℃, the impact strength reaches 150J/m, and the tensile strength before illumination is 498Kg/m2Tensile strength of 412Kg/m after 1000 hours of light irradiation2。
In summary, the invention has the following advantages:
according to the high-strength hard polyvinyl chloride sizing material, the Si-O alternate connection structure in the self structure of the cage-type polysilsesquioxane is utilized, the mechanical property of polyvinyl chloride is effectively improved, the impact resistance is greatly improved, meanwhile, the chemical activity of the surface of the cage-type polysilsesquioxane can promote the cage-type polysilsesquioxane to form strong chemical bond combination with polyvinyl chloride in the extrusion process, and the problems of inorganic particle agglomeration and weak two-phase interface binding force do not exist; in the whole process, the extruded rubber material has an internal permeation effect in a water vapor environment, and hydrolysis reaction is formed in the cage-type polysilsesquioxane. Furthermore, the strong chemical activity on the surface of the cage-type polysilsesquioxane can effectively prevent the polyvinyl chloride from being oxidized, and when active chlorine radicals are formed, the surface of the cage-type polysilsesquioxane can be quickly combined with the chlorine radicals to achieve the effect of fixing the chlorine radicals, so that the damage to the polyvinyl chloride structure is effectively reduced, and therefore, the weather resistance can be improved by adding the cage-type polysilsesquioxane.
The above description is only for the purpose of illustrating preferred embodiments of the present invention and is not to be construed as limiting the invention, and the present invention is not limited to the above examples, and those skilled in the art should also be able to make various changes, modifications, additions or substitutions within the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the high-strength hard polyvinyl chloride colloidal particles is characterized by comprising the following steps: the method comprises the following steps:
s1, performing alkali treatment and acid treatment on the cage-type polysilsesquioxane dispersion liquid, and chloridizing and drying to obtain chlorinated cage-type polysilsesquioxane;
s2, adding polyvinyl chloride into the reaction kettle, and adding cyclohexanone to dissolve the polyvinyl chloride to obtain polyvinyl chloride slurry;
s3, adding the chlorinated cage-type polysilsesquioxane obtained in the step S1 into the polyvinyl chloride slurry obtained in the step 2, and uniformly stirring to obtain a mixture;
s4, extruding and granulating the mixture obtained in the step S3 by using an extruder to obtain prefabricated PVC rubber particles;
s5, placing the prefabricated PVC colloidal particles into a reaction kettle, standing for 2-5h at a constant temperature, taking out the colloidal particles, and drying to obtain the high-strength rigid polyvinyl chloride colloidal particles.
2. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in the step S1, cage type polysilsesquioxane is subjected to ultrasonic treatment to obtain cage type polysilsesquioxane dispersion liquid with the concentration of 30-50 g/L; the cage-type polysilsesquioxane adopts polyfunctional cage-type polysilsesquioxane, and all R groups are reactive groups.
3. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in the step S1, the alkali treatment is ultrasonic treatment for 10-60min by using 0.01-0.04mol/L sodium hydroxide solution, stirring and washing the solution until the solution is neutral and drying the solution, wherein the ultrasonic treatment frequency is 50-80kHz, and the temperature is 50-70 ℃; the acid treatment is to treat for 20-60min by using 0.1-0.5mol/L hydrochloric acid, stir at constant temperature and wash with water; and the stirring temperature at constant temperature is 30-60 ℃.
4. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in the step S1, the chlorination is performed by utilizing a reflux reaction of thionyl chloride and chloroform, wherein the reflux temperature is 70-75 ℃, the mass ratio of the thionyl chloride to the cage-type polysilsesquioxane is 1:3-4, and the volume ratio of the chloroform to the thionyl chloride is 4-6: 1.
5. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in step S2, the polyvinyl chloride in the polyvinyl chloride slurry accounts for 20-50% by mass.
6. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in step S3, the mass of the chlorinated cage-type polysilsesquioxane in the mixture is 10 to 30% of the mass of the polyvinyl chloride.
7. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in step S4, the temperature of the extruder is 170-190 ℃.
8. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in step S5, the reaction kettle is filled with nitrogen and water vapor, and the volume ratio of the nitrogen to the water vapor is 14-20: 1.
9. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in the step 5, the temperature of the constant-temperature standing is 80-90 ℃.
10. The method for preparing high-strength rigid polyvinyl chloride colloidal particles according to claim 1, wherein the method comprises the steps of: in step 5, the drying temperature is 110-.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940800A (en) * | 2022-05-31 | 2022-08-26 | 宁波格亿达光缆科技有限公司 | Antistatic high-flame-retardant PVC optical cable material and preparation method thereof |
| CN116140168A (en) * | 2023-03-13 | 2023-05-23 | 福建煜雄科技有限公司 | Surface treatment process for improving fatigue resistance of metal material |
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| CN112080090A (en) * | 2020-09-15 | 2020-12-15 | 中工恒盛科技有限公司 | Preparation method of cable sleeve |
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| CN112080090A (en) * | 2020-09-15 | 2020-12-15 | 中工恒盛科技有限公司 | Preparation method of cable sleeve |
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| LUCA PALIN 等: "The Use of POSS-Based Nanoadditives for Cable-Grade PVC: Effects on Its Thermal Stability", 《POLYMERS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940800A (en) * | 2022-05-31 | 2022-08-26 | 宁波格亿达光缆科技有限公司 | Antistatic high-flame-retardant PVC optical cable material and preparation method thereof |
| CN114940800B (en) * | 2022-05-31 | 2023-07-21 | 宁波格亿达光缆科技有限公司 | Antistatic high-flame-retardance PVC (polyvinyl chloride) optical cable material and preparation method thereof |
| CN116140168A (en) * | 2023-03-13 | 2023-05-23 | 福建煜雄科技有限公司 | Surface treatment process for improving fatigue resistance of metal material |
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