CN112920533A - CPVC (chlorinated polyvinyl chloride) composition easy to process and preparation method and application thereof - Google Patents

CPVC (chlorinated polyvinyl chloride) composition easy to process and preparation method and application thereof Download PDF

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CN112920533A
CN112920533A CN202110130510.0A CN202110130510A CN112920533A CN 112920533 A CN112920533 A CN 112920533A CN 202110130510 A CN202110130510 A CN 202110130510A CN 112920533 A CN112920533 A CN 112920533A
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cpvc
parts
cpvc composition
resin powder
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张扬
宋科明
余华林
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Guangdong Liansu Technology Industrial Co Ltd
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Priority to PCT/CN2021/083577 priority patent/WO2022160451A1/en
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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
    • C08L27/22—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 modified by chemical after-treatment
    • C08L27/24—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 modified by chemical after-treatment halogenated
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an easily processed CPVC (chlorinated polyvinyl chloride) composition, which comprises the following components in parts by weight: 25-75 parts of CPVC resin powder; 25-75 parts of PVC resin powder; 5-20 parts of CPVC reclaimed materials; 3-8 parts of a calcium-zinc stabilizer; 2-8 parts of nano silicon dioxide; 2-6 parts of an impact modifier; 1.5-2.5 parts of a lubricant; 1-3 parts of ACR processing aid; 2-3 parts of rutile titanium dioxide; 02-0.1 part of pigment; the particle size of the PVC reclaimed material is more than or equal to 40 meshes; the chlorine content in the CPVC resin powder is greater than or equal to 67 wt%. The CPVC pipe has good heat resistance, easy processing and mechanical property. The Vicat softening temperature is more than 90 ℃; the tensile yield strength is more than 49 MPa.

Description

CPVC (chlorinated polyvinyl chloride) composition easy to process and preparation method and application thereof
Technical Field
The invention relates to the technical field of plastic processing, and particularly relates to a CPVC (chlorinated polyvinyl chloride) composition easy to process and a preparation method and application thereof.
Background
The chlorinated polyvinyl chloride resin has excellent performances of high strength, heat resistance, weather resistance, chemical medium corrosion resistance, flame retardance, smoke suppression and the like, and particularly the service temperature can be 40 ℃ higher than that of PVC resin. When the chlorine content is higher, the heat resistance is better, but the processability is poorer, the processability of the CPVC with the chlorine content of more than 67 percent is poorer, the paste is extremely easy to produce, normal production cannot be realized, the processability is generally replaced by reducing the mechanical property and the heat resistance at present, and the chlorine content of the CPVC is 60-63 percent for processing production.
The current production method of PVC pipes uses chlorinated polyvinyl chloride (CPVC) and polyvinyl chloride (PVC) resin as main raw materials, then additives such as a stabilizer, a lubricant, a filler, a toner and the like are selectively added, extrusion molding is carried out by an extruder, and finally the production of the pipes is finished through the working procedures of shaping, cooling, marking, cutting, checking, packaging and the like. However, the chlorine content of CPVC is generally low, which results in poor heat resistance and mechanical properties of PVC pipes, and limits the application of PVC pipes in high heat resistance and high mechanical properties.
Chinese patent (CN111117114A) discloses a PVC heat-resistant pipe and a preparation method thereof, wherein chlorinated polyethylene and PVC resin are mainly added into a system, but the mechanical property and the heat resistance are poor.
Disclosure of Invention
The invention provides an easily processed CPVC composition for overcoming the defects of high processing difficulty, poor mechanical property and poor heat resistance of the CPVC with high chlorine content.
It is another object of the present invention to provide a process for the preparation of said ready-to-process CPVC composition.
It is another object of the present invention to provide the use of said ready-to-process CPVC composition.
In order to achieve the purpose, the invention adopts the technical scheme that:
an easily processable CPVC composition comprises the following components in parts by weight:
Figure BDA0002925007100000011
Figure BDA0002925007100000021
the particle size of the CPVC reclaimed material is more than or equal to 40 meshes;
the chlorine content in the CPVC resin powder is greater than or equal to 67 wt%.
The CPVC resin with the chlorine content of more than or equal to 67 wt% is selected, so that the CPVC composition has very good mechanical property and heat resistance; meanwhile, in order to prevent the defect of poor processability, the processability is improved by adopting a mode of blending PVC resin powder and CPVC reclaimed materials; the CPVC reclaimed material can promote plasticization, reduce melt viscosity and improve processability; wherein, dispersion effect is better when mixing with PVC when selecting the CPVC reclaimed materials when particle size more than or equal to 40 meshes, can greatly improve the processing property, and mechanical properties is better, and in addition, the content of CPVC reclaimed materials can not be too much, too much also can influence the quality of CPVC tubular product, too low then can not realize above-mentioned effect, selects to retrieve the CPVC material also can further realization waste recycling, is favorable to the environmental protection.
The chlorine content in the CPVC resin powder is 67-70 wt%.
The CPVC reclaimed material refers to the condition that the outer diameter is larger or smaller, the pipe is out of roundness is larger or the like due to the processing temperature, speed, vacuum degree and the like of extrusion equipment in the production process of CPVC pipes, and the material of unqualified products of the type can be recycled. The recycling method comprises the steps of crushing the pipe by using a crusher, grinding crushed granules into powder, and enabling the particle size of the reclaimed material to be larger than or equal to 40 meshes, wherein the reclaimed material mainly comprises 60-80 wt% of CPVC resin, 80-100 wt% of PVC resin and 6-12 wt% of impact modifier.
Preferably, the workable CPVC composition comprises the following components in parts by weight:
Figure BDA0002925007100000022
Figure BDA0002925007100000031
preferably, the impact modifier is one of ACR impact modifier, MBS impact modifier or CPE.
Preferably, the lubricant is one of polyethylene wax or oxidized polyethylene wax.
Preferably, the average particle size of the nano silicon dioxide is 10-50 nm.
Preferably, the CPVC composition also contains a pigment, and the pigment is 0.02-0.1 part.
The pigment is one of organic yellow pigment or tangerine powder.
Preferably, the calcium-zinc stabilizer is an environment-friendly calcium-zinc stabilizer.
The invention also provides the workable CPVC composition, comprising the steps of:
s1, weighing CPVC resin powder, PVC resin powder, CPVC reclaimed materials, a calcium-zinc stabilizer, nano silicon dioxide, an impact modifier, a lubricant, an ACR processing aid, rutile titanium dioxide and a pigment in proportion, and uniformly mixing; obtaining a premix;
s2, adding the premix obtained in the step S1 into an extrusion device for extrusion to obtain the CPVC composition.
Preferably, the processing temperature of the extruder is 160-210 ℃.
The CPVC composition easy to process is applied to drinking water pipes and fire fighting pipes.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an easily processed CPVC composition, and CPVC resin with chlorine content more than or equal to 67 wt% is selected from the formula of the CPVC composition, so that CPVC pipes have very good mechanical property and heat resistance; meanwhile, in order to prevent the defect of poor processability, the processability is improved by adopting a mode of blending PVC resin powder and reclaimed materials; the Vicat softening temperature is more than 90 ℃; the tensile yield strength is more than 49 MPa.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
CPVC resin powder a: chlorine content 67 wt%, Korea CPVC-C67;
CPVC resin powder B: chlorine content 68 wt%, Korea CPVC-C68;
CPVC resin powder C: chlorine content 70 wt%, Korea CPVC-C70;
CPVC resin powder D: 60 wt% of chlorine, Korea CPVC-C60;
CPVC reclaimed material A: the grain diameter is 40 meshes;
CPVC reclaimed material B: the grain diameter is 60 meshes;
CPVC reclaimed material C: the grain diameter is 80 meshes;
CPVC reclaimed material D: the grain diameter is 10 meshes;
CPVC reclaimed material E: the grain diameter is 20 meshes;
the preparation method of the CPVC reclaimed material comprises the following steps: the CPVC pipe waste is crushed, ground and sieved by a screen with a specified mesh number to obtain the CPVC pipe waste. The CPVC pipe waste product contains 60 wt% of CPVC resin, 100 wt% of PVC resin and 6-12 wt% of impact modifier.
Calcium zinc stabilizer: bear 161 FP;
nano silicon dioxide: watt's N20;
impact modifier: japanese Brillouin FM-40;
lubricant: taly TL-100;
ACR processing aid: japanese Brillouin PA-40;
rutile type titanium dioxide: kipu titanium NR-950;
pigment: kemeis YM-02.
The workable CPVC pipe of the examples and comparative examples was prepared by a process comprising the steps of:
s1, weighing CPVC resin powder, PVC resin powder, CPVC reclaimed materials, a calcium-zinc stabilizer, nano silicon dioxide, an impact modifier, a lubricant, an ACR processing aid, rutile titanium dioxide and a pigment in proportion, and uniformly mixing; obtaining a premix;
s2, adding the premix obtained in the step S1 into extrusion equipment for extrusion to obtain the CPVC pipe. The processing temperature of the extruder is respectively 1 region 180 ℃, 2 region 175 ℃, 3 region 165 ℃, 4 region 160 ℃, flange section 165 ℃, die body region 160-170 ℃ and die 210 ℃.
Examples 1 to 5
TABLE 1 formulations (parts) of examples 1 to 5
Figure BDA0002925007100000041
Figure BDA0002925007100000051
Examples 6 to 13
TABLE 2 formulations (parts) of examples 6 to 13
Figure BDA0002925007100000052
Examples 14 to 20
TABLE 2 formulations (parts) of examples 14 to 20
Figure BDA0002925007100000053
Figure BDA0002925007100000061
Comparative examples 1 to 4
TABLE 3 formulations (parts) of comparative examples 1 to 4
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
CPVC resin powder C — 50 50 50
CPVC resin powder D 50 — — —
PVC resin powder 50 50 50 50
CPVC reclaimed material B 5 — — —
CPVC reclaimed material D — 5 — —
CPVC reclaimed material E — — 5 —
Calcium zinc stabilizer 5 5 5 5
Nano silicon dioxide 5 5 5 5
Impact modifier 4 4 4 4
Lubricant agent 2 2 2 2
ACR processing aid 1 1 1 1
Rutile type titanium dioxide 2 2 2 2
Pigment (I) 0.05 0.05 0.05 0.05
The above examples and comparative examples were each tested for performance by the following test method:
1. impact strength: GB/T14152-2001;
2. vicat softening temperature: GB/T8802-2001;
3. tensile yield strength: GB/T8004.2-2003;
4. yield: the yield is 100 percent of the total weight of the qualified pipe/the total weight of the raw materials, and the higher the yield is, the better the processing performance is.
TABLE 4 data for examples and comparative examples
Figure BDA0002925007100000071
Figure BDA0002925007100000081
From examples 1-5, the higher the chlorine content of the CPVC resin, the better the mechanical properties, including the higher the Vicat temperature and the tensile strength.
From examples 6 to 17, the lower the proportion of the CPVC resin powder in the formulation, the lower the mechanical strength, but the lower the melt strength, and the easier the processing and molding.
From examples 18 to 20, the higher the proportion of nanosilica in the formulation, the higher the Vicat temperature, but the lower the tensile strength.
From comparative examples 1-4, the particle size of the CPVC recycled material has a large influence on the mechanical property, the particle size is smaller than 40 meshes, or the CPVC recycled material is not added, the mechanical property is greatly reduced, and the requirement of the pipe is not met.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. An easily processable CPVC composition is characterized by comprising the following components in parts by weight:
Figure FDA0002925007090000011
the particle size of the CPVC reclaimed material is more than or equal to 40 meshes;
the chlorine content in the CPVC resin powder is greater than or equal to 67 wt%.
2. A workable CPVC composition according to claim 1 comprising, in parts by weight:
Figure FDA0002925007090000012
3. a ready-to-process CPVC composition according to claim 1 wherein the impact modifier is an ACR impact modifier.
4. A workable CPVC composition according to claim 1 wherein said lubricant is polyethylene wax and low oxidability polyethylene wax.
5. A workable CPVC composition according to claim 1 wherein said nanosilica has an average particle size of from 10 to 50 nm.
6. A ready-to-process CPVC composition as claimed in claim 1, wherein said CPVC composition further comprises a pigment.
7. A ready-to-process CPVC composition according to claim 1, wherein said calcium zinc stabilizer is an environmentally friendly calcium zinc stabilizer.
8. A CPVC composition easy to process as claimed in any one of claims 1 to 7, comprising the steps of:
s1, weighing CPVC resin powder, PVC resin powder, a PVC reclaimed material, a calcium-zinc stabilizer, nano silicon dioxide, an impact modifier, a lubricant, an ACR processing aid, rutile titanium dioxide and a pigment in proportion, and uniformly mixing; obtaining a premix;
s2, adding the premix obtained in the step S1 into an extrusion device for extrusion to obtain the CPVC composition.
9. A process for preparing a workable CPVC composition according to claim 8, wherein said extruder has a processing temperature of 160-210 ℃.
10. Use of the workable CPVC composition of any one of claims 1 to 7 in potable water pipes, fire fighting pipes.
CN202110130510.0A 2021-01-29 2021-01-29 CPVC (chlorinated polyvinyl chloride) composition easy to process and preparation method and application thereof Pending CN112920533A (en)

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CN202110130510.0A CN112920533A (en) 2021-01-29 2021-01-29 CPVC (chlorinated polyvinyl chloride) composition easy to process and preparation method and application thereof
PCT/CN2021/083577 WO2022160451A1 (en) 2021-01-29 2021-03-29 Easy-processing cpvc composition, preparation method therefor and use thereof

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CN115368690B (en) * 2022-09-19 2023-11-28 常州市贝美家居科技有限公司 PVC floor and preparation method thereof

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CN1206274C (en) * 2003-06-26 2005-06-15 四川新元材料工程研究所 Impact resistant active assistant for hard polyvinyl chloride
CN101696306B (en) * 2009-10-26 2011-02-16 宁夏青龙塑料管材有限公司 Heat-resistant wear-resistant PVC pipe
CN102863711B (en) * 2011-07-06 2014-11-26 中国石油化工股份有限公司 Heat-resisting PVC high impact-resisting tubular product and preparation method thereof
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Application publication date: 20210608