CN112574346A - Vinyl chloride copolymer, method for preparing the same, composition comprising the same, and resin article made of the composition - Google Patents

Vinyl chloride copolymer, method for preparing the same, composition comprising the same, and resin article made of the composition Download PDF

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CN112574346A
CN112574346A CN201910931508.6A CN201910931508A CN112574346A CN 112574346 A CN112574346 A CN 112574346A CN 201910931508 A CN201910931508 A CN 201910931508A CN 112574346 A CN112574346 A CN 112574346A
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vinyl chloride
structural unit
mass
based copolymer
formula
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CN112574346B (en
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杨万泰
张先宏
宋长统
马育红
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
    • C08F216/18—Acyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a vinyl chloride-based copolymer, a method for preparing the same, a composition comprising the same, and a resin article made of the composition. The vinyl chloride copolymer comprises: a structural unit (a) based on vinyl chloride, a structural unit (b) based on a monomer represented by the following formula (1), and a structural unit (c), CH based on a monomer represented by the following formula (2)2＝CR1COO(R2O)xR3(1) In the formula (1), R1Selected from hydrogen and C1-6 straight chain or branched chain alkyl; the number x of repeating units is an integer selected from 2 to 20, and each R2Selected from linear or branched alkylene groups having 2 to 10 carbon atoms, which may be the same or differentDifferent; r3Selected from hydrogen and C1-4 linear or branched alkyl, CH2＝CHOR4(2) In the formula (2), R4Selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms, which may be substituted with a halogen atom; the hydrogen atom in the formula (2) may be substituted with a halogen atom.

Description

Vinyl chloride copolymer, method for preparing the same, composition comprising the same, and resin article made of the composition
Technical Field
The invention relates to the field of vinyl chloride resin synthesis, in particular to a vinyl chloride copolymer, a preparation method thereof, a composition comprising the vinyl chloride copolymer and a resin product prepared from the composition.
Background
Polyvinyl chloride (PVC) resin is prepared by polymerizing vinyl chloride monomer (VC) through free radicals, is one of five general resins in synthetic materials, has the yield which is only inferior to that of polyethylene and polypropylene, and belongs to the third general plastic variety in the world. Because of the characteristics of excellent chemical corrosion resistance, chemical stability, thermoplasticity, low manufacturing cost and the like, the PVC resin is widely applied to the fields of buildings, water supply, daily use and biomedicine.
Because the PVC molecular chain has larger polarity, the movement of the molecular chain is limited, and the processing difficulty of the PVC resin is increased. Therefore, plasticizers are added during the processing of polyvinyl chloride to reduce the processing viscosity and improve the flexibility of PVC. At present, phthalate ester (PAEs) plasticizers, represented by dioctyl phthalate (DEHP), are mainly (about 70% or more) used in PVC resin processing. However, PAEs are toxic small-molecule plasticizers, and plasticizer molecules are easy to migrate to the surface of a PVC resin product during the use process of the product, so that the performance of the product is reduced. In particular, in the field of medical products, the small-molecule PAEs plasticizer gradually migrates out of the PVC resin products in the using process of the products and enters blood or body fluid or enters human bodies through other contact ways, and physiological harm is caused. Currently, one of the research hotspots is to develop environmentally friendly non-toxic/low-toxic plasticizers. In this regard, despite the rapid development, it is still difficult to solve the problem of migration of the plasticizer.
In view of the problem of migration of small molecule plasticizers, it is considered that an effective approach is to prepare a vinyl chloride-based copolymer by copolymerizing vinyl chloride with a monomer having a plasticizing function, thereby imparting self-plasticizing performance to a polyvinyl chloride resin. However, vinyl chloride is difficult to copolymerize with other monomers by conventional radical polymerization due to the intrinsic characteristics of vinyl chloride monomer, such as low monomer reactivity, large monomer chain transfer constant, high radical activity, and large reactivity difference with other conventional monomers. Therefore, modified polyvinyl chloride resins are currently mainly prepared by PVC post-graft modification, living polymerization techniques, and the like. In general, for the evaluation of the migration resistance of the modified polyvinyl chloride resin, it is considered whether or not there are easily-migrating components, such as shorter molecular chains or molecular chains having an excessively high content of the plasticizing component, in the resulting resin, which are generated by introducing the plasticizing component into the molecular chains.
For example, in non-patent document 1, a ring-opening reaction of caprolactone and propargyl alcohol is utilized, firstly, polycaprolactone (PCL-Alkyne) with alkynyl as a terminal group is synthesized, then, click reaction is performed on the polycaprolactone and PVC resin (PVC-N3) subjected to azide treatment under the radiation of ultraviolet light, PCL-Alkyne is successfully grafted to a PVC side chain, and DSC tests show that the introduction of PCL significantly reduces the glass transition temperature of the PVC resin, and a good self-plasticizing effect is obtained. However, since the raw materials used in non-patent document 1 are expensive and the production method is complicated, this technique is mainly significant in scientific research and has no value for industrial application. Further, the azide-treated PVC actually sacrifices chlorine atoms in PVC, which greatly contribute to performance, and is disadvantageous for practical use.
For example, non-patent document 2 discloses a method for synthesizing a PVC-g-HPG graft copolymer having self-plasticizing properties by a click reaction using azide-treated PVC and an alkynyl-containing hyperbranched polyglycidyl ether. Due to the covalent bonding of HPG-C6 to PVC, the amorphous, dendritic structure of HPG-C6 and the plurality of polyether segments, the PVC-g-HPG graft copolymer shows excellent flexibility and mechanical properties. When the grafting amount of the HPG-C6 is 9 percent, the elongation at break is as high as 900 percent, the migration rate of the plasticizing component is almost zero, and the PVC resin with the self-plasticizing effect is realized. However, this technique has practical problems such as complicated process, high cost, and unsuitability for mass production, similar to the case of non-patent document 1.
For example, non-patent document 3 reports that a PVC-BA and PVC-EHA graft polymer is synthesized by modifying polyvinyl chloride using unstable chlorine in the PVC molecular chain as a reaction site and by graft-polymerizing and modifying PVC resin with butyl acrylate and 2-ethylhexyl acrylate by ATRP method. However, non-patent document 3 does not pay attention to the self-plasticizing performance. In addition, the transition metal compound tends to remain in the resin obtained by this technique, resulting in poor durability of the resin in actual use.
For example, in non-patent document 4, a polyvinyl chloride resin is modified by reactive blending, and a molten state blend of in-situ polymerization such as PVC/PMMA, PVC/PVAc, PVC/PBA, and PVC/PEHA is obtained in a twin-screw extruder from a PVC suspension having a monomer, an initiator, and a crosslinking agent adsorbed thereon. The reaction temperature in the extruder is 180 ℃, and the obtained product is mostly low molecular weight polymer, thereby playing the role of plasticizing PVC. However, this technique has the following problems: the reaction temperature is up to 180 ℃, the reaction time is long, and the PVC is easy to decompose. In addition, the reactive extrusion has high requirements on equipment, so that the cost is high and the industrial production is difficult to realize.
For example, in non-patent document 5, a butyl acrylate-vinyl chloride copolymer is prepared by suspension polymerization of a butyl acrylate monomer and vinyl chloride. However, according to the teaching of non-patent document 5, the amount of butyl acrylate used is only 10% or less. This is because when this value reaches 10%, the resulting resin tends to be blocked. In addition, since the content of the butyl acrylate-based structural unit that can be incorporated into the resulting resin is small, the self-plasticizing property is limited and it is difficult to relatively freely adjust the properties of the resin according to the actual use.
For example, non-patent document 6 describes that suspension copolymerization of VC and BA is studied by a one-electron transfer-degenerate chain transfer living radical polymerization (SET-DTLRP) method, and a polyvinyl chloride-polybutyl acrylate random copolymer (PVC-PBA) having a uniform copolymerization composition is synthesized by a one-step method, and DMTA results show that the Tg of a PVC-PBA vinyl chloride copolymer resin is also reduced from 70 ℃ to 25 ℃ as the content of PBA is gradually increased from 10% to 40%. Although living polymerization methods are suitable for adjusting the structure of the resulting copolymer resin, such techniques are demanding on the production process, costly, and not industrially applicable.
As described above, most of the presently disclosed techniques are only in the scientific research stage, and the industrial utility value is not high; and techniques suitable for industrial production tend to have difficulty in achieving excellent self-plasticization and poor control over product structure.
On the other hand, in industrial production, in order to improve self-plasticization of polyvinyl chloride, attempts have been made to introduce vinyl ether-based monomer units into the molecular chain of polyvinyl chloride, for example, typically to obtain a copolymer of vinyl isobutyl ether and vinyl chloride (generally referred to as a chlorohydrin resin). Although the conventional epichlorohydrin resin improves the flexibility of the vinyl chloride resin, the processing can be carried out without adding a plasticizer only under the condition of low requirement on the tensile elongation at break, and when the product with high tensile elongation at break needs to be prepared, the plasticizing effect of the vinyl ether monomer in the prior art is insufficient, so that a large amount of additional plasticizer still needs to be added. In addition, most of the conventional epichlorohydrin resins are obtained by emulsion polymerization and exist in the form of emulsion or paste resins, resulting in a limited range of applications thereof.
Documents of the prior art
Non-patent document
Non-patent document 1: eur. polymer. j.,2015,66, 282-289.
Non-patent document 2: rapid commu., 2016,37, 2045-.
Non-patent document 3: J.Polym.Sci.part A.Polym.Chem.2003, 41, 457-
Non-patent document 4: Polymer.adv.Technol.2005, 16, 495-.
Non-patent document 5: chloralkali of china, 2013, 2, 17-22.
Non-patent document 6: eur. Polymer.J., 2015,73, 202-211.
Disclosure of Invention
Problems to be solved by the invention
In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a vinyl chloride-based copolymer having excellent self-plasticization and processing lubricity and adjustable mechanical properties, and on the basis thereof, a product made therefrom has excellent biological properties.
The present invention also aims to provide a method for producing the vinyl chloride copolymer, a resin composition comprising the vinyl chloride copolymer, and an article made of the resin composition.
Means for solving the problems
In order to achieve the above object, the present invention provides a vinyl chloride copolymer having the following features [1] to [10], a method for producing the vinyl chloride copolymer, a resin composition comprising the vinyl chloride copolymer, and a product made of the resin composition.
[1] A vinyl chloride copolymer comprising: a structural unit (a) based on vinyl chloride, a structural unit (b) based on a monomer represented by the following formula (1), and a structural unit (c) based on a monomer represented by the following formula (2),
CH2＝CR1COO(R2O)xR3 (1)
in the formula (1), R1Selected from hydrogen and C1-6 straight chain or branched chain alkyl; the number x of repeating units is an integer selected from 2 to 20, and each R2Selected from linear or branched alkylene groups having 2 to 10 carbon atoms, which may be the same or different; r3Selected from hydrogen and C1-4 linear or branched alkyl,
CH2＝CHOR4 (2)
in the formula (2), R4Selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms, which may be substituted with a halogen atom; the hydrogen atom in the formula (2) may be substituted with a halogen atom.
[2] The vinyl chloride copolymer according to [1], wherein the content of the structural unit (a) is 50 to 98% by mass based on the total mass of the vinyl chloride copolymer.
[3] The vinyl chloride copolymer according to [1] or [2], wherein the content of the structural unit (b) is 2 to 30% by mass based on the total mass of the vinyl chloride copolymer.
[4] The vinyl chloride-based copolymer according to any one of [1] to [3], wherein the content of the structural unit (c) is 1 to 30% by mass based on the total mass of the vinyl chloride-based copolymer.
[5]According to [1]To [4]]The vinyl chloride-based copolymer of the formula (1), wherein R is1Selected from hydrogen and C1-4 straight chain or branched chain alkyl; the number x of repeating units is an integer selected from 2 to 15, and each R2The alkylene groups may be the same or different and are selected from linear or branched alkylene groups having 2 to 6 carbon atoms.
[6] The vinyl chloride-based copolymer according to any one of [1] to [5], which has a number average molecular weight of 40000 to 250000.
[7] The vinyl chloride-based copolymer according to any one of [1] to [6], which is a random copolymer.
[8] A method for producing a vinyl chloride-based copolymer according to any one of [1] to [7], comprising: copolymerizing raw materials including vinyl chloride, the monomer represented by the formula (1), and the monomer represented by the formula (2).
[9] A vinyl chloride-based resin composition comprising the vinyl chloride-based copolymer according to any one of [1] to [7 ].
[10] A resin article made of the vinyl chloride-based resin composition according to [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a vinyl chloride-based copolymer having excellent self-plasticization and processing lubricity and adjustable mechanical properties. By copolymerizing vinyl chloride with the monomer represented by the above formula (1) and the monomer represented by the above formula (2) to introduce a plasticizing segment and a lubricating segment into the molecular chain of polyvinyl chloride, the resulting vinyl chloride-based copolymer can be well plasticized and shaped at the time of processing even without adding a plasticizer, thereby avoiding the deterioration of the performance of the resin article and environmental pollution due to the migration of the plasticizer; and also reduces melt viscosity and adhesion to processing machinery during processing.
In addition, although the mechanism is not clear, the presence of the monomer represented by the above formula (1) allows vinyl chloride to be copolymerized with a wide range of amount of the monomer represented by the above formula (2), and the vinyl chloride-based copolymer of the present invention has adjustable mechanical properties, in other words, it may be rigid PVC which is generally recognized in the art, and it may also be flexible PVC which is generally recognized in the art.
On the basis, the monomer shown in the formula (1) and the monomer shown in the formula (2) also provide biocompatibility. Therefore, the product made of the vinyl chloride-based copolymer of the present invention may not only contain no plasticizer but also have good biological properties (e.g., no toxicity, no coagulation, etc.), thereby allowing the product made of the vinyl chloride-based copolymer of the present invention to have good biological properties useful for medical use.
The present invention also provides a method for producing the above vinyl chloride-based copolymer, which realizes copolymerization of vinyl chloride and each comonomer by a simple method advantageous for industrial production. The preparation method of the invention can be implemented by various polymerization methods to obtain polymerization products with different forms, thereby expanding the application range of vinyl chloride copolymers based on vinyl ether monomers.
The present invention further provides a vinyl chloride-based resin composition comprising the above vinyl chloride-based copolymer and a resin article made of the resin composition.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the term "(meth) acrylate" is a concept covering both methacrylate and acrylate.
In the present specification, a repeating unit directly formed by polymerization of a monomer and a unit formed by chemically converting a part or all of substituents of the repeating unit formed by polymerization of a monomer into other substituents are collectively referred to as a "structural unit".
In the present specification, "%" means mass% unless otherwise specified.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Reference throughout this specification to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," or the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< vinyl chloride copolymer >
The vinyl chloride-based copolymer of the present invention comprises: a structural unit (a) based on vinyl chloride, a structural unit (b) based on a monomer represented by the following formula (1), and a structural unit (c) based on a monomer represented by the following formula (2).
CH2＝CR1COO(R2O)xR3 (1)
In the formula (1), R1Selected from hydrogen and C1-6 straight chain or branched chain alkyl; the number x of repeating units is an integer selected from 2 to 20, and each R2Is selected fromStraight-chain or branched alkylene groups having 2 to 10 carbon atoms, which may be the same or different; r3Selected from hydrogen and C1-4 linear or branched alkyl.
CH2＝CHOR4 (2)
In the formula (2), R4Selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms, which may be substituted with a halogen atom; the hydrogen atom in the formula (2) may be substituted with a halogen atom.
The respective structural units in the vinyl chloride-based copolymer of the present invention are described in detail below.
(structural Unit (a))
The structural unit (a) is a vinyl chloride-based structural unit.
(structural Unit (b))
The structural unit (b) is a structural unit based on a monomer represented by the following formula (1).
CH2＝CR1COO(R2O)xR3 (1)
In the vinyl chloride-based copolymer of the present invention, the structural unit (b) provides a plasticizing effect to reduce the polarity and rigidity of the polymer molecular chain, improving processability. The monomer represented by the above formula (1) has good copolymerizability with vinyl chloride, and can copolymerize with vinyl chloride in a wide range of proportions even in a conventional radical polymerization system.
In the formula (1), R1The alkyl group is selected from hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms, preferably from hydrogen and a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen and/or a methyl group.
In the formula (1), the number x of the repeating units is an integer selected from 2 to 20, and from the viewpoint of obtaining more excellent self-plasticization and further suppressing the migration of the segment, the number x of the repeating units is preferably an integer selected from 2 to 15, more preferably an integer selected from 2 to 10. Each R2Selected from linear or branched alkylene groups having 2 to 10 carbon atoms, more excellent self-plasticization property and further inhibited segment migrationFrom the viewpoint of the compatibility, the alkyl group is preferably selected from a linear or branched alkylene group having 2 to 6 carbon atoms, and more preferably from a linear or branched alkylene group having 2 to 4 carbon atoms. Each R2May be the same or different.
R3Selected from hydrogen and C1-4 linear or branched alkyl.
When each R is2Meanwhile, specific examples of the monomer represented by the above formula (1) include, but are not limited to, polyethylene glycol methyl ether (meth) acrylate, polyethylene glycol ethyl ether (meth) acrylate, polyethylene glycol propyl ether (meth) acrylate, polyethylene glycol butyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol methyl ether (meth) acrylate, polypropylene glycol ethyl ether (meth) acrylate, polypropylene glycol propyl ether (meth) acrylate, polypropylene glycol butyl ether (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol methyl ether (meth) acrylate, polybutylene glycol ethyl ether (meth) acrylate, polybutylene glycol propyl ether (meth) acrylate, polybutylene glycol butyl ether (meth) acrylate, and polybutylene glycol mono (meth) acrylate. These monomers may be used alone or in combination of two or more.
When each R is2At the same time, the monomer represented by the above formula (1) may be represented by the structural formula represented by the formula (1 a):
CH2＝CR1COO(R2aO)a(R2bO)bR3(1a)，
preferably, in formula (1a), R1And R3As defined above; r2aIs ethylene, R2bThe propylene group has a repeating unit number a of 1 to 3 and a repeating unit number b of 1 to 12.
(structural Unit (c))
The structural unit (c) is a structural unit based on a monomer represented by the following formula (2).
CH2＝CHOR4 (2)
In the vinyl chloride-based copolymer of the present invention, the structural unit (c) provides an auxiliary plasticizing action and a processing lubricating action, as well as good biocompatibility, excellent molecular structure stability, good miscibility with other resins, good wettability with fillers such as pigments, and the like.
In the formula (2), R4The alkyl group is selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms, and these groups may be substituted with a halogen atom such as chlorine, bromine, fluorine, or the like. Preferably, R4The alkyl group is selected from a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched cycloalkyl group having 3 to 8 carbon atoms, and a linear or branched hydroxyalkyl group having 1 to 8 carbon atoms, and these groups may be substituted with a halogen atom such as chlorine, bromine, fluorine, or the like. Further, the hydrogen atom in formula (2) (means "CH" in formula (2))2The hydrogen atom in ═ CH — ") may be substituted with a halogen atom such as chlorine, bromine, or fluorine.
Examples of the monomer represented by the above formula (2) include, but are not limited to, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl t-butyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl n-pentyl ether, vinyl cyclopentyl ether, vinyl cyclohexyl ether, 5-hydroxypentyl vinyl ether, 4-hydroxypentyl vinyl ether, 3-hydroxypentyl vinyl ether, 2-hydroxypentyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether. Among them, vinyl n-butyl ether, vinyl isobutyl ether, 3-hydroxypropyl vinyl ether and 4-hydroxybutyl vinyl ether are preferred. These monomers may be used alone or in combination of two or more.
(content of structural units (a), (b) and (c))
In the present invention, the content of each of the structural unit (a), the structural unit (b) and the structural unit (c) is not particularly limited, and may be appropriately selected depending on the use of the vinyl chloride copolymer.
In the present invention, in some preferred embodiments, the content of the structural unit (a) is preferably 50 to 98 mass%, more preferably 55 to 95 mass%, and still more preferably 60 to 90 mass% with respect to the total mass of the vinyl chloride-based copolymer. When the content of the structural unit (a) is more than the above-mentioned preferable range, the processability and the biological properties of the resulting vinyl chloride-based copolymer tend to be deteriorated. When the content of the structural unit (a) is less than the above range, the mechanical properties of the resulting vinyl chloride-based copolymer tend to deteriorate.
In the present invention, in some preferred embodiments, the content of the structural unit (b) is preferably 2 to 30% by mass, more preferably 3 to 28% by mass, and still more preferably 5 to 25% by mass, relative to the total mass of the vinyl chloride-based copolymer. When the content of the structural unit (b) is more than the above range, although a significant plasticizing effect is exerted on the vinyl chloride-based copolymer, the mechanical properties of the resulting vinyl chloride-based copolymer tend to be lowered; when the content of the structural unit (b) is less than the above range, the self-plasticization property, the processability and the biological property of the resulting vinyl chloride-based copolymer tend to be deteriorated.
The content of the structural unit (c) is preferably 1 to 30% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 28% by mass, relative to the total mass of the vinyl chloride-based copolymer, from the viewpoints of further improving self-plasticization, processing lubricity, mechanical properties, and reducing cost.
In other preferred embodiments, the respective contents of the structural unit (a), the structural unit (b) and the structural unit (c) simultaneously satisfy the above-mentioned ranges. For example, the content of the structural unit (a) is preferably 50 to 98% by mass, the content of the structural unit (b) is preferably 2 to 30% by mass, and the content of the structural unit (c) is preferably 1 to 30% by mass, based on the total mass of the vinyl chloride-based copolymer.
In other preferred embodiments, the total content of the structural unit (b) and the structural unit (c) is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, relative to the total mass of the vinyl chloride-based copolymer, from the viewpoints of better improvement in self-plasticization, processing lubricity, mechanical properties, and cost reduction. For example, in some embodiments in which the vinyl chloride-based copolymer of the present invention is rigid, the total content of the structural unit (b) and the structural unit (c) is preferably 2 to 22% by mass, more preferably 2 to 20% by mass, and still more preferably 3 to 18% by mass. In some embodiments where the vinyl chloride-based copolymer of the present invention is soft, the total content of the structural unit (b) and the structural unit (c) is preferably more than 22 to 40% by mass, more preferably 24 to 40% by mass.
(structural units based on other monomers)
The vinyl chloride-based copolymer of the present invention may optionally include a structural unit based on another monomer in addition to the structural unit (a) based on vinyl chloride, the structural unit (b) based on the monomer represented by formula (1), and the structural unit (c) based on the monomer represented by formula (2) within a range that does not impair the technical effects of the present invention.
The other monomer is not particularly limited as long as it can be copolymerized with any one of vinyl chloride, the monomer represented by formula (1), and the monomer represented by formula (2).
In the present invention, it is preferable that examples of the structural unit based on other monomer include, without being limited to, a structural unit based on a fluorine-containing (meth) acrylate-based monomer, a structural unit based on a maleimide-based monomer, a structural unit based on a acrylonitrile-based monomer, and a structural unit based on a carboxyl-containing monomer. These structural units may be present in the vinyl chloride-based copolymer of the present invention alone or in combination to impart desired properties to the vinyl chloride-based copolymer as necessary.
Structural units based on fluorine-containing (meth) acrylate monomers
The structural unit based on the fluorine-containing (meth) acrylate monomer is a structural unit based on a monomer represented by the following formula (3).
CH2＝CR5COOR6 (3)
In the formula (3), R5Selected from hydrogen and methyl, R6The fluorinated alkyl group is selected from a linear or branched fluoroalkyl group having 1 to 18 carbon atoms, a fluorocycloalkyl group having 3 to 18 carbon atoms, and a fluorophenyl group, and is preferably selected from a linear or branched fluoroalkyl group having 1 to 12 carbon atoms, a fluorocycloalkyl group having 3 to 12 carbon atoms, and a fluorophenyl group. Further, the hydrogen atom in formula (3) (means "CH" in formula (3))2Hydrogen atom in ═ may be substituted with a halogen atom such as chlorine, bromine, fluorine, etc.
Examples of the monomer represented by the above formula (3) include, but are not limited to, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, pentafluorophenyl (meth) acrylate, hexafluorobutyl (meth) acrylate, heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, nonafluorohexyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, and tridecafluoroctyl (meth) acrylate. Among them, trifluoroethyl (meth) acrylate, pentafluorophenyl (meth) acrylate and hexafluorobutyl (meth) acrylate are preferable. These monomers may be used alone or in combination of two or more.
When the vinyl chloride-based copolymer of the present invention has a structural unit based on the monomer of formula (3) described above, it can provide excellent processing lubricity (e.g., reduction in adhesion to a twin roll or a screw, reduction in melt viscosity, etc.) and antibacterial/antifouling properties of the product.
Structural unit based on maleimide monomer
Examples of maleimide monomers that form building blocks based on maleimide monomers include, without limitation, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N-phenylmaleimide. These monomers may be used alone or in combination of two or more.
Structural units based on acrylonitrile monomers
Examples of the acrylonitrile-based monomer forming the structural unit based on the acrylonitrile-based monomer include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. These monomers may be used alone or in combination of two or more.
Building blocks based on carboxyl-containing monomers
Examples of the carboxyl group-containing monomer forming the structural unit based on the carboxyl group-containing monomer include, without limitation, acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These monomers may be used alone or in combination of two or more.
(glass transition temperature (Tg))
The glass transition temperature of the vinyl chloride copolymer of the present invention can embody the structural characteristics of the copolymer and can be used to exhibit self-plasticization.
The vinyl chloride-based copolymer of the present invention preferably has only one glass transition temperature from the viewpoint of obtaining more excellent self-plasticization and processability. Further, the glass transition temperature is not particularly limited in general. The glass transition temperature is preferably less than 80 ℃ and more preferably-20 to 75 ℃ and can be suitably adjusted depending on the type (hard or soft) of the vinyl chloride copolymer. However, when the glass transition temperature is not less than the above upper limit, the self-plasticization property of the vinyl chloride-based copolymer of the present invention tends to deteriorate.
In the present invention, the glass transition temperature can be measured by a dynamic thermomechanical analyzer (DMTA).
(number average molecular weight)
The number average molecular weight of the vinyl chloride copolymer of the present invention is not particularly limited, and may be appropriately selected according to the application. The number average molecular weight of the vinyl chloride-based copolymer of the present invention is preferably 40000 to 250000, more preferably 50000 to 220000, and still more preferably 50000 to 200000, from the viewpoint of achieving both more excellent mechanical properties and lower cost. When the number average molecular weight is less than the above range, mechanical properties of the copolymer resin such as tensile strength and tensile elongation at break tend to decrease. When the number average molecular weight is larger than the above range, it is necessary that the polymerization temperature tends to be excessively low, resulting in low conversion and increased production cost.
In the present invention, the number average molecular weight can be measured in terms of polystyrene by Gel Permeation Chromatography (GPC).
(Properties)
The physical properties of the vinyl chloride copolymer of the present invention are not particularly limited, and may be appropriately adjusted depending on the use of the vinyl chloride copolymer.
Polyvinyl chloride is generally processed with addition of a plasticizer, as understood in the art of resin processability, and therefore, polyvinyl chloride resins are classified into rigid polyvinyl chloride (for example, having a plasticizer content of less than 20%) and soft polyvinyl chloride (for example, having a plasticizer content of 20% or more) and the like according to the content of the plasticizer added thereto, and are expressed as differences in physical properties such as mechanical properties. However, since the vinyl chloride-based copolymer of the present invention can be processed excellently even without adding a plasticizer, the polyvinyl chloride-based copolymer is mainly classified according to the range of tensile elongation at break in the present invention. In the present invention, a vinyl chloride-based copolymer having a tensile elongation at break of 140% or less is hard, and a vinyl chloride-based copolymer having a tensile elongation at break of more than 140% is soft.
In the present invention, the tensile elongation at break of the vinyl chloride-based copolymer is measured in accordance with the test method of GB/T1040-2006. The tensile elongation at break of the vinyl chloride copolymer of the present invention is preferably 10% or more, and can be appropriately adjusted as needed. In some embodiments where the vinyl chloride-based copolymer of the present invention is rigid, the tensile elongation at break is preferably 10 to 140%, and more preferably 12 to 135%. In some embodiments where the vinyl chloride-based copolymer of the present invention is soft, the tensile elongation at break of the vinyl chloride-based copolymer of the present invention is preferably more than 140%, more preferably more than 160%, still more preferably more than 180%, still more preferably more than 200%.
In the present invention, the tensile strength of the vinyl chloride-based copolymer is preferably more than 6MPa, more preferably more than 8MPa, according to the test method of GB/T1040-.
In the present invention, the hardness of the vinyl chloride copolymer is not particularly limited, and the hardness test method is performed according to GB/T2411-2008, and shore A or shore D is performed as required. Generally, where the hardness (shore a) is greater than 90, the hardness may be expressed by shore D hardness. In some embodiments, the hardness (shore a) is less than 80, suitable for the test on shore a; in other embodiments, the hardness (shore D) is greater than 70, when tested according to shore D.
< method for producing vinyl chloride copolymer >
The method for producing a vinyl chloride copolymer of the present invention is a method for producing the vinyl chloride copolymer, including: copolymerizing raw materials including vinyl chloride, the monomer represented by the formula (1) and the monomer represented by the formula (2).
Details of vinyl chloride, the monomer represented by formula (1), the monomer represented by formula (2), and other monomers are described above and will not be described herein.
Examples of copolymerization reactions of the present invention include, without limitation, block polymerization, random polymerization, graft polymerization, gradient polymerization. Among them, random polymerization is preferable from the viewpoint of more favorably exhibiting the technical effects of the present invention, that is, the molecular chain of the vinyl chloride-based copolymer of the present invention preferably has a random structure. More preferably, the vinyl chloride-based copolymer of the present invention is a random copolymer.
The mechanism of the production method is not particularly limited as long as the vinyl chloride-based copolymer of the present invention can be obtained, and a general radical polymerization method, a living radical polymerization method, and the like can be employed. However, the preparation method of the vinyl chloride-based copolymer of the present invention is based on a general radical polymerization mechanism from the viewpoint of facilitating industrial production.
As the polymerization method, any polymerization method that can be carried out by a radical polymerization mechanism, for example, emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, slurry polymerization, gas phase polymerization, interface polymerization, and the like can be used. From the viewpoints of adjustment of molecular weight and copolymerization composition and productivity, suspension polymerization, bulk polymerization and emulsion polymerization are preferably employed.
(bulk polymerization method)
The bulk polymerization process of the present invention is a bulk polymerization process known in the art. Specifically, the bulk polymerization method of the present invention is a polymerization method in which a dispersion medium is not contained in a polymerization system, and preferably, the bulk polymerization method is carried out by polymerizing each monomer used in the present invention in the presence of an initiator.
In the case of the bulk polymerization method, the order of addition and the manner of addition of the monomers are not limited, and the monomers may be added together or may be added in portions in any combination.
Specific examples of initiators suitable for use in the bulk polymerization process include, without limitation: azo initiators such as azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, and the like; organic peroxide initiators, for example, t-butyl peroxyneoheptanoate, t-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, dicetyl peroxydicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxypivalate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, dibutyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, t-butyl 2-ethylhexanoate, ditetradecyl peroxydicarbonate, t-butyl peroxyacetate, cumyl peroxyneodecanoate, di-t-butyl peroxide, cyclohexylsulfonyl peroxide, dibenzoyl peroxide, diisobutyl peroxide, 1,3, 3-tetramethylbutyl peroxyneodecanoate, tert-butyl peroxydicarbonate, di-butyl peroxydicarbonate, dicetyl, tert-butyl peroxydicarbonate, and mixtures thereof, Di-3-methoxybutyl peroxydicarbonate, 1,3, 3-tetramethylbutyl peroxypivalate, and the like. These radical initiators may be used alone or in combination of two or more. In particular, free radical initiators having a decomposition temperature of less than 80 ℃ are preferred.
The amount of the initiator to be used is preferably 0.001 to 4% by mass, more preferably 0.01 to 2% by mass, based on the total mass of the monomers.
The polymerization conditions may be appropriately selected depending on the monomer composition, the decomposition temperature of the initiator, and the like. The polymerization temperature is preferably 0 to 100 ℃, more preferably 10 to 90 ℃, and most preferably 30 to 80 ℃. The polymerization time is preferably 1 to 72 hours, more preferably 1 to 24 hours, and most preferably 1 to 12 hours.
(suspension polymerization method)
The suspension polymerization process of the present invention is a suspension polymerization process well known in the art. Preferably, the suspension polymerization method of the present invention is carried out in a state where agitation is applied to the polymerization system.
The dispersion medium in the suspension polymerization process may be water or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent may include, without limitation: alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, etc.; ketones such as acetone, butanone, cyclohexanone, etc.; polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1, 3-dimethylimidazolidinone, and epsilon-caprolactam; amides such as formamide, N-methylformamide, formamide and N, N-dimethylformamide; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol; propylene carbonate and ethylene carbonate.
The dispersion medium is preferably water from the viewpoint of easy recovery. As for water, various forms such as tap water, deionized water, distilled water, and the like can be employed.
The dispersant in the suspension polymerization method may be any known dispersant in the art, such as anionic dispersant, cationic dispersant, nonionic dispersant, and polymeric dispersant.
Specific examples of the dispersant may include, without limitation: water-soluble organic high molecular substances, for example, partially hydrolyzed polyvinyl alcohol, salts of polyacrylic acid or polymethacrylic acid, synthetic high molecules such as maleic anhydride/styrene copolymer, cellulose derivatives such as methylcellulose, hydroxymethylcellulose and hydroxypropylcellulose, natural high molecules such as gelatin, protein, starch and sodium alginate; and water-insoluble inorganic powders such as magnesium carbonate, calcium carbonate, barium sulfate, calcium phosphate, talc, kaolin; and the like. These dispersants may be used alone or in combination of two or more. In view of the particle size, shape, transparency and film-forming property of the product, it is preferable to use a water-soluble organic high molecular substance, and it is more preferable to use a mixture of polyvinyl alcohol and a cellulose derivative. The amount of the dispersant used is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on 100 parts by mass of the dispersion medium.
The monomer concentration in the system is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, based on the total mass of the dispersion medium.
In the case of the suspension polymerization method, the order of addition and the manner of addition of the monomers are not limited, and the monomers may be added together or may be added in portions in any combination.
The kind of the initiator, the amount of the initiator used, and the polymerization conditions (polymerization temperature, polymerization time, etc.) each range suitable for the suspension polymerization method are the same as those in the above-mentioned "(bulk polymerization method)", and will not be described in detail herein.
(emulsion polymerization method)
The emulsion polymerization process of the present invention is well known in the art. Preferably, the emulsion polymerization method of the present invention is carried out in a state where agitation is applied to the polymerization system.
The kind of the dispersion medium is the same as in the above "(suspension polymerization method)", and will not be described in detail herein.
The monomer concentration in the system is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, based on the total mass of the dispersion medium.
The emulsifier in the emulsion polymerization process may be an emulsifier well known in the art. Specific examples of the emulsifier of the present invention may include, but are not limited to: nonionic emulsifiers such as polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene styrenated phenyl ether, polyoxyalkylene benzylated phenyl ether, polyoxyalkylene cumylphenyl ether, fatty acid polyglycol ether, polyoxyalkylene sorbitan fatty acid ester, sorbitan fatty acid ester and the like; anionic emulsifiers such as fatty acid soaps, rosin acid soaps, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfate ester salts, alkyl sulfosuccinates, and sulfate ester salts, phosphate ester salts, ether carboxylates, sulfosuccinates of nonionic emulsifiers having polyoxyalkylene chains, and the like; cationic emulsifiers, such as stearyltrimethylammonium salt, cetyltrimethylammonium salt, lauryltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkyldimethylhydroxyethylammonium salt and the like.
The amount of the emulsifier used is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, based on 100 parts by mass of the dispersion medium.
In addition, the emulsion polymerization process of the present invention may not use an emulsifier, i.e., the emulsion polymerization process of the present invention may be based on a self-emulsion polymerization process.
In the case of the emulsion polymerization method, the order of addition and the manner of addition of the monomers are not limited, and the monomers may be added together or may be added in portions in any combination.
Specific examples of initiators suitable for use in the emulsion polymerization process include, without limitation: the initiator described in the above "(bulk polymerization method)"; a redox initiator; persulfates, such as ammonium persulfate, potassium persulfate, and the like. These initiators may be used alone or in combination.
The amount of the initiator to be used is preferably 0.001 to 4% by mass, more preferably 0.01 to 2% by mass, based on the total mass of the monomers.
The polymerization conditions may be appropriately selected depending on the monomer composition, the decomposition temperature of the initiator, and the like. The polymerization temperature is preferably 10 to 90 ℃, and most preferably 30 to 80 ℃. The polymerization time is preferably 1 to 72 hours, more preferably 1 to 24 hours, and most preferably 1 to 12 hours.
< vinyl chloride resin composition >
The vinyl chloride resin composition of the present invention includes the above vinyl chloride copolymer.
The vinyl chloride-based resin composition of the present invention may optionally include other components in addition to the vinyl chloride-based copolymer of the present invention, and examples of the other components include other resins such as other vinyl chloride-based resins, acrylic-based resins, vinyl-based resins, polyester-based resins such as polyethylene terephthalate, styrene-based resins, fluorine resins, silicone resins, polyamide-based resins, polyimide-based resins, and the like; rubbers such as styrene-butadiene rubber, nitrile rubber, butyl rubber, chloroprene rubber, isoprene rubber, butadiene rubber, ethylene propylene diene rubber, silicone rubber; examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyvinyl chloride-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and fluoropolymer-based thermoplastic elastomers. They may be used alone or in combination of two or more. The content of the other components is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 0 part by mass, relative to 100 parts by mass of the vinyl chloride-based resin composition.
The vinyl chloride-based resin composition of the present invention may further optionally include various additives generally known in the art, such as fillers, pigments, plasticizers, ultraviolet absorbers, light stabilizers, delusterants, surfactants, leveling agents, surface conditioners, degassing agents, heat stabilizers, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, antibacterial agents, foaming agents, crosslinking agents, and the like, at any content. They may be used alone or in combination of two or more. In some preferred embodiments, the vinyl chloride-based resin composition of the present invention does not include a plasticizer since the vinyl chloride-based copolymer of the present invention has excellent self-plasticization.
The vinyl chloride-based resin composition of the present invention can be prepared by a method generally known in the art. For example, in the case where the vinyl chloride-based resin composition of the present invention is used for the production of a molded article, all the components constituting the vinyl chloride-based resin composition of the present invention are mixed using standard mixing equipment such as a Banbury or Brabender mixer, an extruder, a kneader, and a two-roll mixer. In the case where the vinyl chloride-based resin composition of the present invention is used for producing a coating film or the like, all the components constituting the vinyl chloride-based resin composition of the present invention are mixed by using a dispersing machine such as a homogenizer, a paint shaker, an ultrasonic dispersing device, a stirrer having a stirring blade, a magnetic stirrer, a high-speed dispersing device, a sand mill, a ball mill, a hammer mill, or the like.
The preparation method of the composition is not particularly limited regardless of the form of the composition, and the above-mentioned mixing may be performed in a single-stage or multi-stage manner according to the desired composition of the composition. The mixing temperature and mixing speed for the above-mentioned mixing are also not particularly limited and may be appropriately selected depending on the desired composition of the composition.
< resin article >
The resin product of the present invention is a PVC molded article (hard or soft) or a coated article made of the above vinyl chloride resin composition. In some embodiments, the resin article of the present invention is preferably a melt-molded article, for example, a molded article obtained by extrusion molding, injection molding, blow molding, mold (press) molding, calender molding, or the like.
The resin article of the present invention can be used for various purposes known in the art, for example, PVC sheets, PVC pipes, PVC profiles, PVC containers, children's toys, etc.
In some preferred embodiments, the resin article of the present invention may be a product used in the medical field, for example, luer fittings, indwelling needles, specimen containers, drip sets, medical packaging PVC rigid sheets, infusion tubes, blood transfusion bags, medical catheters, dialysis tubes, dialysis bags, surgical gloves, artificial organs, and the like.
Examples
The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.
< evaluation method >
The composition ratio of each structural unit of the vinyl chloride-based copolymer, the number average molecular weight and molecular weight distribution (PDI) of the copolymer, mechanical properties, processing lubricity, self-plasticization, migration resistance, and biological properties were determined by the following methods.
(composition ratio of copolymer)
The composition ratio of the copolymer was measured by Brookfield AV400 NMR spectrometer (THF-d8 as a solvent).
(number average molecular weight and molecular weight distribution (PDI) of copolymer)
The number average molecular weight and molecular weight distribution of the copolymer were determined by Waters-1515 gel chromatography using THF as eluent and polystyrene as standard.
(mechanical Properties)
100 parts of the vinyl chloride-based copolymers and 2 parts of the methyl tin mercaptide heat stabilizer of each of examples and comparative examples were kneaded with a two-roll kneader, and then hot-pressed at 175 ℃ for 5 minutes and cold-pressed for 5 minutes to obtain sample pieces. The prepared sample wafer is cut into dumbbell-shaped sample bars, and the tensile strength and the elongation at break are measured according to GB/T1040-.
(processing lubricity)
The vinyl chloride-based copolymers of examples and comparative examples were investigated for their processability (including maximum torque, minimum torque, equilibrium torque, plasticizing time, plasticizing temperature, thermal decomposition time, etc.) by using a torque rheometer model RM-200/300. In the invention, the quality of the processing performance of the PVC dry blend can be measured by calculating the melting factor F, and the larger the F is, the better the processing lubricating performance is. The calculation formula is as follows: f-maximum torque2/(minimum torque x plastication time).
It should be noted that: f >0.785 is defined as optimal, 0.735< F <0.785 as optimal, 0.700< F <0.735 as good, and F <0.700 as poor.
(self-plasticization)
The self-plasticization was evaluated by the glass transition temperature. The sample pieces were prepared in the same manner as in the evaluation of the mechanical properties described above. Cutting the obtained sample into sample strips with the width of 5mm and the length of 75mm, and testing by using DMTA 2980, wherein the testing mode is a stretching mode, the frequency of the testing condition is 1Hz, and the temperature range is-60-100 ℃.
(migration resistance)
In the present invention, the evaluation of the migration resistance is based on the presence or absence of a molecular chain which is easily migrated due to the introduction of a plasticizing segment into the molecular chain in the vinyl chloride copolymer.
The vinyl chloride-based copolymers of examples and comparative examples were sampled according to the sampling method in the evaluation of mechanical properties to obtain sample pieces, and each sample piece was cut in parallel into 2 groups of 5 small pieces, weighed and recorded. And (3) respectively soaking the 2 groups of cut sample blocks in ethanol and water at normal temperature for 48h, finally taking out, drying in a 50 ℃ oven for 24h, and weighing. The percentage of the mass difference before and after soaking (in ethanol or water) of the sample piece to the mass of the sample piece before soaking was calculated, and the average of the percentages was defined as the migration rate. It should be noted that the migration rate should be less than or equal to 0.1%.
(biological)
The sample pieces were prepared in the same manner as in the evaluation of the mechanical properties described above. The plaques were tested for hemolysis and cytotoxicity according to GB/T16886.5 and GB/T16886.12.
It is noted that the hemolysis ratio values in GB/T16886.5 and GB/T16886.12 require R < 5%. In the present invention, 2.5% < R < 5% is defined as good, 0.5% < R < 2.5% is defined as excellent, and R < 0.5% is defined as optimal.
< example 1>
Into a stainless steel microreactor having an internal volume of 200ml and equipped with a stirring blade, 100g of deionized water, 10.4g of a 2 mass% aqueous PVA solution, 0.042g of hydroxypropyl methylcellulose, 0.05g of azobisisobutyronitrile, 18.9g of polypropylene glycol monomethacrylate having a molecular weight of 375 (PPGMA-375, in the case where x is 5 in formula (1)), and 2.7g of vinyl isobutyl ether (VIBE) were charged, and the atmosphere in the microreactor was replaced with nitrogen gas for 5 minutes. Then 32.4g of VC monomer is introduced into the reaction kettle. After pre-stirring for 60min, heating to 70 ℃ to start polymerization, wherein the mass ratio of VC to PPGMA-375 (VC: 60:35: 5) is defined as the monomer feeding mass ratio, and the polymerization reaction time is 8 hours. After completion of the polymerization, the unreacted VC monomer was recovered, and the polymerization product was washed with a large amount of deionized water and ethanol alternately to obtain 50.5g of a vinyl chloride-based copolymer as white solid particles, which had a composition of: the content of the structural unit (a) was 60.2 mass%, the content of the structural unit (b) was 35.6 mass%, and the content of the structural unit (c) was 4.2 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 2>
A vinyl chloride-based copolymer (48.2 g) was obtained as white solid particles in the same manner as in example 1, except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE 60:14:26 and the polymerization reaction time was 7.5 hours, and had a composition: the content of the structural unit (a) was 60.4% by mass, the content of the structural unit (b) was 15.4% by mass, and the content of the structural unit (c) was 24.2% by mass, based on the total mass of the vinyl chloride-based copolymer.
< example 3>
49.6g of a vinyl chloride-based copolymer in the form of white solid particles having a composition of, by weight, 49.6g as obtained in example 1 was prepared by changing the charge mass ratio of VC to PPGMA-375 and VIBE to 60:24:16 and the polymerization time to 7.5 hours: the content of the structural unit (a) was 60.6% by mass, the content of the structural unit (b) was 24.6% by mass, and the content of the structural unit (c) was 14.8% by mass, based on the total mass of the vinyl chloride-based copolymer.
< example 4>
A vinyl chloride-based copolymer (48.6 g) was obtained as white solid particles in the same manner as in example 1, except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE 60:4:36 and the polymerization reaction time was 8.5 hours, and the composition thereof was: the content of the structural unit (a) was 60.0 mass%, the content of the structural unit (b) was 5.1 mass%, and the content of the structural unit (c) was 34.9 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 5>
49.9g of a vinyl chloride-based copolymer in the same manner as in example 1 was obtained as white solid particles, except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE of 70:6:24 and the polymerization reaction time was 8.5 hours, and the composition thereof was: the content of the structural unit (a) was 69.0 mass%, the content of the structural unit (b) was 6.8 mass%, and the content of the structural unit (c) was 24.2 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 6>
50.6g of a vinyl chloride-based copolymer in the form of white solid particles having a composition of, by weight, 50.6g as obtained in example 1 was prepared by changing the charge mass ratio of VC to PPGMA-375 and VIBE to 70:15:15 and the polymerization reaction time to 7.5 hours: the content of the structural unit (a) was 69.4% by mass, the content of the structural unit (b) was 15.6% by mass, and the content of the structural unit (c) was 15.0% by mass, based on the total mass of the vinyl chloride-based copolymer.
< example 7>
A vinyl chloride-based copolymer (48.2 g) was obtained as white solid particles, having a composition in the same manner as in example 1, except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE of 80:1.5:18.5 and the polymerization reaction time was 9.0 hours: the content of the structural unit (a) was 79.8 mass%, the content of the structural unit (b) was 1.6 mass%, and the content of the structural unit (c) was 18.6 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 8>
49.7g of a vinyl chloride-based copolymer in the same manner as in example 1 was obtained as white solid particles, except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE of 80:6:14 and the polymerization reaction time was 7.5 hours, and the composition thereof was: the content of the structural unit (a) was 79.8 mass%, the content of the structural unit (b) was 6.3 mass%, and the content of the structural unit (c) was 13.9 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 9>
51.2g of a vinyl chloride-based copolymer in the form of white solid particles having a composition of, by weight, 51.2g as obtained in example 1 was prepared by changing the charge mass ratio of VC to PPGMA-375 and VIBE to 80:10:10 and the polymerization reaction time to 7.5 hours: the content of the structural unit (a) was 80.0 mass%, the content of the structural unit (b) was 10.3 mass%, and the content of the structural unit (c) was 9.7 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 10>
52.6g of a vinyl chloride-based copolymer in the form of white solid particles having a composition as described in example 1 was obtained except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE of 90:5:5 and the polymerization reaction time was 7.5 hours: the content of the structural unit (a) was 90.2 mass%, the content of the structural unit (b) was 5.0 mass%, and the content of the structural unit (c) was 4.8 mass%, based on the total mass of the vinyl chloride-based copolymer.
< example 11>
A vinyl chloride-based copolymer (52.0 g) was obtained as white solid particles in the same manner as in example 1, except that the charge mass ratio of VC to PPGMA-375 and VIBE was changed to VC: PPGMA-375: VIBE of 90:8:2 and the polymerization reaction time was 7.5 hours, and had a composition: the content of the structural unit (a) was 90.2 mass%, the content of the structural unit (b) was 7.8 mass%, and the content of the structural unit (c) was 2.0 mass%, based on the total mass of the vinyl chloride-based copolymer.
< comparative example 1>
A vinyl chloride-based copolymer (45.3 g) was obtained as white solid particles in the same manner as in example 1, except that PPGMA-375 was not used, the charge mass ratio of VC to VIBE was 80:20, and the polymerization reaction time was 8.0 hours: the content of the structural unit (a) was 82.1% by mass and the content of the structural unit (c) was 17.9% by mass, based on the total mass of the vinyl chloride-based copolymer.
< comparative example 2>
A vinyl chloride copolymer (50.5 g) was obtained as white solid particles, having a composition of, except that VIBE was not used, the charge mass ratio of VC to PPGMA-375 was set to 90:10, and the polymerization reaction time was 8.0 hours, in the same manner as in example 1: the content of the structural unit (a) was 89.5% by mass and the content of the structural unit (b) was 10.5% by mass, based on the total mass of the vinyl chloride-based copolymer.
In the above examples and comparative examples, the monomer compositions involved in the polymerization were different from each other. The polymerization time varies depending on the monomer composition in order to complete the reaction as much as possible.
In addition, the suspension polymerization product having good morphology, i.e., the vinyl chloride-based copolymer of the present invention can be obtained by the industrially conventional technique in each of the examples of the present invention.
As can be seen from the results of tables 1 and 2, the vinyl chloride-based copolymer obtained in each example satisfying the requirements of the present invention satisfies the conventional requirements of various kinds of PVC while having adjustable mechanical properties as well as excellent self-plasticization, migration resistance, biological properties, processing lubricity. According to the visual observation, the specimens made of the copolymer resins obtained in examples 1 to 11 were excellent in transparency.
As is clear from the comparison between examples 1 to 11 and comparative example 1, in comparative example 1, the molecular weight of the copolymer not containing the structural unit (b) is reduced, the elongation at break is drastically reduced, and the plasticizing performance is also reduced.
As is clear from comparison between examples 10 and 11 and comparative example 2, the copolymer of comparative example 2 not containing the structural unit (c) has a low melt factor and poor processing lubricity.
TABLE 1
Figure BDA0002220400270000251
TABLE 2
Figure BDA0002220400270000261
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like within the spirit and scope of the present invention should be included.

Claims (10)

1. A vinyl chloride copolymer comprising: a structural unit (a) based on vinyl chloride, a structural unit (b) based on a monomer represented by the following formula (1), and a structural unit (c) based on a monomer represented by the following formula (2),
CH2＝CR1COO(R2O)xR3 (1)
in the formula (1), R1Selected from hydrogen and C1-6 straight chain or branched chain alkyl; the number x of repeating units is an integer selected from 2 to 20, and each R2Selected from linear or branched alkylene groups having 2 to 10 carbon atoms, which may be the same or different; r3Selected from hydrogen and C1-4 linear or branched alkyl,
CH2＝CHOR4 (2)
in the formula (2), R4Selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms, which may be substituted with a halogen atom; the hydrogen atom in the formula (2) may be substituted with a halogen atom.
2. The vinyl chloride-based copolymer according to claim 1, wherein the content of the structural unit (a) is 50 to 98% by mass based on the total mass of the vinyl chloride-based copolymer.
3. The vinyl chloride-based copolymer according to claim 1 or 2, wherein the content of the structural unit (b) is 2 to 30% by mass based on the total mass of the vinyl chloride-based copolymer.
4. The vinyl chloride-based copolymer according to any one of claims 1 to 3, wherein the content of the structural unit (c) is 1 to 30% by mass based on the total mass of the vinyl chloride-based copolymer.
5. The vinyl chloride-based copolymer according to any one of claims 1 to 4, wherein R in the formula (1)1Selected from hydrogen and C1-4 straight chain or branched chain alkyl; the number x of repeating units is an integer selected from 2 to 15, and each R2The alkylene groups may be the same or different and are selected from linear or branched alkylene groups having 2 to 6 carbon atoms.
6. The vinyl chloride-based copolymer according to any one of claims 1 to 5, wherein the number average molecular weight of the vinyl chloride-based copolymer is 40000 to 250000.
7. The vinyl chloride-based copolymer according to any one of claims 1 to 6, wherein the vinyl chloride-based copolymer is a random copolymer.
8. A method for producing a vinyl chloride-based copolymer according to any one of claims 1 to 7, comprising: copolymerizing raw materials including vinyl chloride, the monomer represented by the formula (1), and the monomer represented by the formula (2).
9. A vinyl chloride-based resin composition comprising the vinyl chloride-based copolymer according to any one of claims 1 to 7.
10. A resin article characterized by being produced from the vinyl chloride-based resin composition according to claim 9.
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