CN117820535A - Soft vinyl chloride copolymer, process for producing the same, vinyl chloride resin composition, and resin product - Google Patents

Soft vinyl chloride copolymer, process for producing the same, vinyl chloride resin composition, and resin product Download PDF

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CN117820535A
CN117820535A CN202311795041.XA CN202311795041A CN117820535A CN 117820535 A CN117820535 A CN 117820535A CN 202311795041 A CN202311795041 A CN 202311795041A CN 117820535 A CN117820535 A CN 117820535A
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vinyl chloride
mass
structural unit
carbon atoms
based copolymer
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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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Abstract

The present invention relates to a soft vinyl chloride copolymer, a method for producing the same, a vinyl chloride resin composition, and a resin article. The soft 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),in the formula (1), R 1 Selected from hydrogen and alkyl groups having 1 to 6 carbon atoms; r is R 2 Selected from alkyl groups having 1 to 5 carbon atoms; each R is 3 Independently selected from hydrogen and alkyl groups of 1 to 22 carbon atoms, but not simultaneouslyIs a hydrogen gas which is used as a hydrogen gas,in the formula (2), R 4 Selected from hydrogen and methyl, R 5 Selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxyalkyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 18 carbon atoms, and a cycloalkyl group having 3 to 18 hetero atoms; the content of the structural unit (b) is 1 to 20 mass% and the content of the structural unit (c) is more than 19 mass% and 60 mass% or less relative to 100 mass% of the total mass of the soft vinyl chloride copolymer.

Description

Soft vinyl chloride copolymer, process for producing the same, vinyl chloride resin composition, and resin product
Technical Field
The invention relates to the field of vinyl chloride resin synthesis, in particular to a soft vinyl chloride copolymer, a preparation method thereof, a vinyl chloride resin composition and a resin product.
Background
Polyvinyl chloride (PVC) resin is formed by polymerizing vinyl chloride monomer (VC) through free radicals, is one of five general resins in synthetic materials, and has the yield inferior to polyethylene and polypropylene, and is the third largest general plastic variety worldwide. PVC resin is widely used in the fields of construction, water supply, daily use and biomedical applications due to its excellent chemical resistance, chemical stability, thermoplasticity, low manufacturing cost and the like.
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 melt viscosity and improve the flexibility of the PVC. Currently, phthalate esters (PAEs) plasticizers typified by dioctyl phthalate (DEHP) are mainly used (about 70% or more) in PVC resin processing. However, PAEs are toxic small-molecule plasticizers, and plasticizer molecules are easily migrated to the surface of the product during the use of PVC resin products, resulting in the degradation of product performance. In particular, in the field of medical products, small molecule pae plasticizers gradually migrate out of the product during the use of PVC resin products, enter blood or body fluids, or enter the human body in other contact ways, causing physiological hazards. At present, one of the research hotspots is to develop environment-friendly non-toxic/low-toxic plasticizers. In this regard, despite rapid developments, the problem of plasticizer migration remains difficult to solve.
In view of the problem of the 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 properties to a polyvinyl chloride resin. However, vinyl chloride is difficult to copolymerize with other monomers by ordinary radical polymerization due to its own characteristics such as low monomer reactivity, large monomer chain transfer constant, high radical reactivity, and large reactivity ratio difference from other conventional monomers. Thus, modified polyvinyl chloride resins are currently prepared mainly by post-PVC graft modification, living polymerization techniques, and the like. In general, for evaluation of the migration resistance of a modified polyvinyl chloride resin, it is considered whether or not an easily migrating component, such as a shorter molecular chain or a molecular chain having an excessively high content of a plasticizing component, is present in the resulting resin due to the introduction of the plasticizing component into the molecular chain.
For example, in non-patent document 1, polycaprolactone (PCL-Alkyne) with an alkynyl end group is synthesized by utilizing ring-opening reaction of caprolactone and propargyl alcohol, then click reaction is carried out on the polycaprolactone and the azide-treated PVC resin (PVC-N3) under the radiation of ultraviolet light, PCL-Alkyne is successfully grafted onto a PVC side chain in a covalent manner, and DSC test shows that the introduction of PCL remarkably 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, the main significance of this technique is scientific research, and it has no industrial application value. Further, the azide-treated PVC actually sacrifices chlorine atoms in the PVC that contribute greatly to the properties, which is disadvantageous for practical use.
For example, non-patent document 2 reports that an active polymerization technique is used to modify polyvinyl chloride, and an ATRP method is used to graft-polymerize and modify a PVC resin with butyl acrylate and 2-ethylhexyl acrylate by using unstable chlorine on a PVC molecular chain as a reaction site, thereby synthesizing a PVC-BA and PVC-EHA graft polymer. However, non-patent document 2 does not pay attention to self-plasticizing performance. In addition, transition metal compounds tend to remain in the resin obtained by this technique, resulting in poor durability of the resin in practical use.
For example, in non-patent document 3, a polyvinyl chloride resin is modified by reactive blending, and a PVC suspension having a monomer, an initiator, and a crosslinking agent adsorbed thereon is obtained in a twin-screw extruder to obtain an in-situ polymerized melt blend such as PVC/PMMA, PVC/PVAc, PVC/PBA, PVC/PEHA. The reaction temperature in the extruder is 180 ℃, so that the obtained product is mostly a polymer with low molecular weight, and the PVC has the effect of plasticizing, however, the PVC is easy to cause thermal decomposition under the process route, and the requirement on equipment is high, so that the industrial production is difficult.
For example, in non-patent document 4, butyl acrylate-vinyl chloride copolymer is prepared by suspension polymerization of butyl acrylate monomer and vinyl chloride. However, according to the teaching of non-patent document 5, the amount of butyl acrylate is only 10% or less. This is because when the value reaches 10%, the resulting resin tends to be agglomerated. In addition, the self-plasticizing properties are limited due to the low content of structural units based on butyl acrylate which can be incorporated into the resulting resin.
For example, non-patent document 5 describes that suspension copolymerization of VC and BA is studied by a single 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 the PVC-PBA vinyl chloride copolymer resin is also lowered from 70 ℃ to 25 ℃ as the PBA content is gradually increased from 10% to 40% in the polyvinyl chloride-polybutyl acrylate random copolymer. Although the living polymerization method is suitable for adjusting the structure of the obtained copolymer resin, the technology has high requirements on the production process and high cost, and in addition, the residual metal ions in the product have the defects of complex post-treatment and the like, and the technology has no industrial application value.
However, when the ordinary radical polymerization is adopted, the polymerization of vinyl chloride and acrylic ester copolymer, especially vinyl chloride and butyl acrylate, vinyl chloride and isooctyl acrylate, can obviously improve the toughness and elongation at break of the product, but due to the difference of the polymerization activity of acrylic ester monomer and vinyl chloride, the homopolymer of acrylic ester is easy to generate in the copolymerization process, and the homopolymer of acrylic ester existing in the system causes the opacity of the product due to the problem of compatibility with polyvinyl chloride.
In addition, conventionally known vinyl chloride-vinyl acetate copolymers (i.e., vinyl chloride/vinyl acetate copolymers) are also generally considered to have self-plasticizing properties. However, in practical use, the self-plasticization of the vinyl chloride-vinyl acetate copolymer resin is still to be improved. Moreover, the vinyl chloride resin has high hardness and is generally not suitable as a soft vinyl chloride resin. In addition, since the tensile strength of the vinyl chloride-vinyl acetate copolymer is low, it is often used as an adhesive or as a processing aid used for the production of a melt-molded article, and is rarely used as a main material of the melt-molded article.
As mentioned above, most of the presently disclosed techniques are only in the scientific research stage, and the industrial practical value is not high; while techniques suitable for industrial production tend to be difficult to achieve excellent self-ductility and have poor control over the structure of the product.
Further, from the viewpoint of industrial application, it is also desired that the processability of the vinyl chloride-based polymer having self-plasticity is excellent. This is because, even if plasticization is smooth (the plasticization is achieved by the external plasticizer and/or the polymer has self-plasticization), the plasticized melt may not be easily processed, and other processing aids (for example, ACR) may be additionally added.
The present inventors have also proposed a soft vinyl chloride copolymer comprising a vinyl chloride-based structural unit (a) and a CH-based structural unit in a specific ratio 2 ＝CR 1 COO(R 2 O) x R 3 Structural units (b) and optionally CH-based monomers shown 2 ＝CR 4 COOR 5 The structural unit (c) of the monomer shown (refer to patent document 1). The copolymer can be obtained by a simple method and has excellent self-plasticity, transparency and biological property. However, the structural units (b) are relatively hydrophilic, and thus the copolymers have limited application in applications where hydrophilicity is undesirable, even where water resistance is required.
Accordingly, there is a need for a vinyl chloride-based copolymer that is compatible with conventional soft resins in terms of mechanical properties that are compatible with self-plasticization, processability, biology, transparency, and can be used in applications where water resistance is required.
Prior art literature
Non-patent literature
Non-patent document 1: eur.Polym.J.,2015,66,282-289.
Non-patent document 2: J.Polym.Sci.: part A: polym.chem.,2003,41,457-3462
Non-patent document 3: polym.Adv.technology.2005, 16,495-504.
Non-patent document 4: chinese chlor-alkali, 2013,2, 17-22.
Non-patent document 5: eur.Polym.J.,2015,73,202-211.
Patent literature
Patent document 1: CN 112574348A
Disclosure of Invention
Problems to be solved by the invention
In view of the above-described problems of the prior art, an object of the present invention is to provide a soft vinyl chloride copolymer having excellent biological properties, water resistance, transparency, self-plasticization, processability and mechanical properties.
The present invention also provides a method for producing the above vinyl chloride-based copolymer, a resin composition comprising the above vinyl chloride-based copolymer, and an article produced from the resin composition.
Solution for solving the problem
According to the intensive studies of the present inventors, it was found that the above technical problems can be solved by the implementation of the following technical scheme:
[1] a soft vinyl chloride-based 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),
in the formula (1), R 1 Selected from hydrogen and alkyl groups having 1 to 6 carbon atoms; r is R 2 Selected from alkyl groups having 1 to 5 carbon atoms; each R is 3 Independently selected from hydrogen and alkyl groups of 1 to 22 carbon atoms, but not simultaneously hydrogen,
in the formula (2), R 4 Selected from hydrogen and methyl, R 5 Selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxyalkyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 18 carbon atoms, and a cycloalkyl group having 3 to 18 hetero atoms;
The content of the structural unit (b) is 1 to 20 mass% and the content of the structural unit (c) is more than 19 mass% and 60 mass% or less relative to 100 mass% of the total mass of the soft vinyl chloride copolymer.
[2]According to [1]]The soft vinyl chloride copolymer is represented by the formula (1), wherein R 1 Selected from hydrogen and methyl; r is R 2 Selected from alkyl groups having 1 to 4 carbon atoms; each R is 3 Independently selected from hydrogen and alkyl groups having 1 to 18 carbon atoms, but not simultaneously hydrogen.
[3]According to [1]]Or [2 ]]The soft vinyl chloride copolymer is represented by the formula (2), wherein R 5 Selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 hetero atoms.
[4] The soft vinyl chloride-based copolymer according to any one of [1] to [3], wherein the content of the structural unit (a) is 40 to 79.5 mass% relative to 100 mass% of the total mass of the soft vinyl chloride-based copolymer.
[5] The soft vinyl chloride-based copolymer according to any one of [1] to [4], wherein the total content of the structural unit (b) and the structural unit (c) is more than 20% by mass and 60% by mass or less relative to 100% by mass of the total mass of the soft vinyl chloride-based copolymer.
[6] The soft vinyl chloride-based copolymer according to any one of [1] to [5], wherein the mass ratio of the structural unit (b) to the structural unit (c) in the soft vinyl chloride-based copolymer is 1/40 to 1/1.
[7] The soft vinyl chloride-based copolymer according to any one of [1] to [6], wherein the soft vinyl chloride-based copolymer has a tensile elongation at break of more than 140%; the number average molecular weight of the soft vinyl chloride copolymer is 40000-250000.
[8] A process for producing the soft vinyl chloride-based copolymer according to any one of [1] to [7], which comprises: copolymerizing a raw material comprising 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 soft 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 soft vinyl chloride copolymer having excellent biological properties, water resistance, transparency, self-plasticizing properties, processability and mechanical properties.
By copolymerizing vinyl chloride with the monomer represented by the above formula (1) and the monomer represented by the above formula (2) in a specific ratio, the resulting vinyl chloride-based copolymer has excellent mechanical properties satisfying the soft vinyl chloride-based resin; meanwhile, on the one hand, since a plasticizing segment is incorporated in the molecular chain of polyvinyl chloride, the resulting vinyl chloride-based copolymer can be well plasticized, i.e., exhibits self-plasticizing properties, even without the addition of a plasticizer during processing, and on the other hand, can be made to exhibit excellent processability even without the addition of a processing aid (in the present invention, "excellent processability" means the property of easy handling of the melt during melt plasticizing/forming).
In particular, the soft vinyl chloride-based copolymer of the present invention has excellent transparency.
Further, the soft vinyl chloride-based copolymer of the present invention can exhibit better water resistance because it can contain no hydrophilic ether chain group (polyoxyalkylene group) as shown in patent document 1.
In addition, the vinyl chloride-based copolymer of the present invention itself is not biologically toxic. Moreover, since the articles made from the vinyl chloride-based copolymer of the present invention may not contain a plasticizer, the articles may also have good biological properties (e.g., no cytotoxicity, good biocompatibility, no coagulation, etc.).
The invention also provides a method for preparing the vinyl chloride copolymer, which realizes the copolymerization of vinyl chloride and various comonomers through a simple method favorable for industrial production.
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
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by the use of "above" and "below" refer to ranges including the end point values.
In this specification, the numerical ranges indicated by the use of "greater than" and "less than" refer to ranges that do not include the end values.
In the present specification, "%" means weight percent unless otherwise specified.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process, or the meaning of having a certain component or not having a certain component.
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.
In the present specification, "alkyl" or "alkylene" means unsubstituted "alkyl" or "alkylene" in a straight chain, branched or cyclic form, and "aryl" or "arylene" means "aryl" or "arylene" having no substituent other than alkyl on an aromatic ring (benzene ring, naphthalene ring, etc.).
In the present specification, the "structural unit" in a polymer refers to a polymerized unit derived from a monomer formed by polymerizing the monomer, and a polymerized unit formed by converting a part of the polymerized unit into another structure by treating the polymer.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
In the present specification, the meaning of "selected from A, B, … and E" means at least one selected from the group consisting of each item (A, B, …, E), and any one of each item and any combination of two or more of each item are covered.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, 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 elements may be combined in any suitable manner in the various embodiments.
< vinyl chloride copolymer >
The soft vinyl chloride 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),
in the formula (1), R 1 Selected from hydrogen and alkyl groups having 1 to 6 carbon atoms; r is R 2 Selected from alkyl groups having 1 to 5 carbon atoms; each R is 3 Independently selected from hydrogen and alkyl groups of 1 to 22 carbon atoms, but not simultaneously hydrogen,
in the formula (2), R 4 Selected from hydrogen and methyl, R 5 Selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxyalkyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 18 carbon atoms, and a cycloalkyl group having 3 to 18 hetero atoms;
the content of the structural unit (b) is 1 to 20 mass% and the content of the structural unit (c) is more than 19 mass% and 60 mass% or less relative to 100 mass% of the total mass of the soft vinyl chloride copolymer.
The structural units of the vinyl chloride-based copolymer of the present invention will be described in detail below.
(structural unit (a))
The structural unit (a) is a structural unit based on vinyl chloride.
(structural unit (b))
The structural unit (b) is a structural unit based on a monomer represented by the following formula (1).
In the vinyl chloride-based copolymer of the present invention, the structural unit (b) provides self-plasticization, processability, water resistance, and transparency. The monomer represented by the above formula (1) has good copolymerizability with vinyl chloride and the monomer represented by the following formula (2), and even in a general radical polymerization system, it can copolymerize with vinyl chloride and the monomer represented by the following formula (2) in a wide range of proportions and improve the copolymerizability between vinyl chloride and the monomer represented by the following formula (2), and the molecular chain composition of the resulting copolymer is relatively uniform. Thus, the vinyl chloride-based copolymer of the present invention may have desired properties.
In the formula (1), R 1 Selected from hydrogen and alkyl groups having 1 to 6 carbon atoms, preferably selected from hydrogen and linear or branched alkyl groups having 1 to 6 carbon atoms, more preferably hydrogen and/or methyl groups, and still more preferably hydrogen.
In the formula (1), R 2 From the viewpoint of obtaining more excellent self-plasticizability and processability, an alkyl group having 1 to 5 carbon atoms is more preferable. In addition, as R 2 The alkyl group of (2) is preferably linear or branched. From the viewpoint of obtaining further excellent self-moldability and workability, R 2 Further preferred are methyl, ethyl or/and propyl.
In the formula (1), each R 3 Independently selected from hydrogen and alkyl groups having 1 to 22 carbon atoms, but not simultaneously hydrogen. From the viewpoint of obtaining more excellent self-plasticization and processability, each R 3 More preferably independently selected from hydrogen and an alkyl group having 1 to 20 carbon atoms, and still more preferably independently selected from hydrogen and an alkyl group having 1 to 18 carbon atoms. When each R is 3 And when the alkyl groups are simultaneously, the alkyl groups can be the same or different. In addition, as R 3 The alkyl group of (2) is preferably linear or branched.
In some preferred embodiments, from the standpoint of better achieving the desired effect of the present invention, two R 3 The total carbon number of (2) is preferably 1 to 24, more preferably 2 20. Here, when two R' s 3 When one is hydrogen, "two R 3 The total carbon number "of (2) is another R as an alkyl group 3 Carbon number of (2); when two R 3 When each is an alkyl group having 1 to 22 carbon atoms, "two R groups 3 The "total carbon number of two alkyl groups" is the total carbon number of two alkyl groups.
When two R 3 Specific examples of the monomer represented by the above formula (1) when one is hydrogen include, but are not limited to: vinyl 2-methylpropionate, vinyl 2-methylbutyrate, vinyl 2-methylpentanoate, vinyl 2-methylhexanoate, vinyl 2-ethylbutyrate, vinyl 2-ethylpentanoate, vinyl 2-ethylhexanoate (V2 EH), vinyl 2-ethylheptanoate, vinyl 2-propylvalerate, and the like. These monomers may be used alone or in combination of two or more.
When two R 3 Specific examples of the monomer represented by the above formula (1) include, but are not limited to, monomers represented by the following formula (1-X) (X is 1 to 9) when each is an alkyl group having 1 to 24 carbon atoms (since commercial products of the present monomer are sometimes a mixture of isomers and only two R's are labeled 3 Since the total carbon number of (2) is equal to or greater than that of the monomer represented by the following formulae (1-1) to (1-8), the structure of a part of the monomers is composed of only two R 3 Is represented by the total carbon number of (2), without specifically listing two R' s 3 Respective structures):
In the formula (1-1), two R 3 Is 2, two R 3 Are all methyl groups; in the formula (1-2), two R 3 Is 3 in total carbon number, one R 3 Is methyl, another R 3 Is ethyl; in the formula (1-3), two R 3 Is 7 in total carbon number; in the formula (1-4), two R 3 Is 9 in total carbon number; in the formula (1-5), two R 3 The total carbon number of (2) is 10; in the formula (1-6), two R 3 The total carbon number of (2) is 11; in the formula (1-7), two R 3 Is 13 in total carbon number; in the formula (1-8), two R 3 Is 20 in total carbon number; in the formula (1-9), two R 3 The total carbon number of (2). These monomers may be singlyThe components may be used alone or in combination of two or more.
Note that, for convenience of expression, in the description of the present invention and the examples described below, the carbon adjacent to the carbon of the carbonyl group (i.e., the carbon adjacent to R in formula (1)) in the exemplary monomers listed as the monomer shown in formula (1) above 2 And two R 3 Attached carbon), if the carbon numbers of the respective alkyl groups are different, the alkyl group having the largest carbon number is taken as one R 3 And the alkyl group with the least carbon number is taken as R 2 . For example, in vinyl 2-ethylhexanoate, one R 3 Is butyl, another R 3 Is H, R 2 Is ethyl, and in vinyl 2, 2-dimethylhexanoate, one R 3 Is butyl, another R 3 Is methyl, R 2 Is methyl.
(structural unit (c))
The structural unit (c) is a structural unit based on a monomer represented by the following formula (2).
In the vinyl chloride-based copolymer of the present invention, the structural unit (c) provides plasticization, improves mechanical properties, water resistance, and reduces costs of the vinyl chloride-based copolymer.
In the formula (2), R 4 Selected from hydrogen and methyl.
In the formula (2), R 5 Selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, hydroxyalkyl groups having 1 to 18 carbon atoms, alkoxyalkyl groups having 1 to 18 carbon atoms, aminoalkyl groups having 1 to 18 carbon atoms, and cycloalkyl groups having 3 to 18 atoms having heteroatoms such as oxygen, nitrogen, sulfur, and the like. In some preferred embodiments, R is from the viewpoint of better achieving the technical effects of the present invention 5 Selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 hetero atoms.
In addition, as R 5 The alkyl, hydroxyalkyl, alkoxyalkyl, or aminoalkyl groups of (2) are preferably straight-chainIn the form of a branch or a chain.
Note that, "hydroxyalkyl" means an alkyl group on which an arbitrary hydrogen atom is substituted with a hydroxyl group; "alkoxyalkyl" means an alkyl group substituted with an alkoxy group at any hydrogen atom thereof; "aminoalkyl" means an alkyl group having an amino group substituted by an optional hydrogen atom thereon.
Specific examples of the monomer represented by the above formula (2) include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, tert-pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, undecyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy-4-hydroxy-butyl (meth) acrylate, 2-hydroxy-hexyl (meth) acrylate, 6-hydroxy-octyl (meth) acrylate, 8-hydroxy-hexyl (meth) acrylate 10-hydroxydecyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like. These monomers may be used alone or in combination of two or more.
From the viewpoints of copolymerizability with each monomer and adjustment of self-plasticizing property, soft demand and mechanical properties of the resulting copolymer, (meth) acrylate monomers having a homopolymer glass transition temperature of less than 60 ℃ are preferred; among them, at least one selected from methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and hexyl (meth) acrylate is more preferable.
(content of structural units (a), (b) and (c))
The content of the other units such as the structural unit (a) is not particularly limited as long as the content of the structural unit (b) in the vinyl chloride-based copolymer of the present invention is 1 to 20% by mass, and the content of the structural unit (c) is more than 19% by mass and 60% by mass or less, and may be appropriately selected depending on the use of the vinyl chloride-based copolymer.
In the present invention, when the content of the structural unit (b) is more than 20 mass%, the vinyl chloride-based copolymer becomes hard and, on the contrary, does not satisfy the requirements of mechanical properties (for example, elongation at break, etc.) of the soft vinyl chloride-based resin; when the content of the structural unit (b) is less than 1% by mass, the self-plasticizability and processability of the resulting vinyl chloride-based copolymer are deteriorated, the transparency is also lowered, and the copolymerization reaction for obtaining the copolymer is difficult. In some preferred embodiments, the content of the structural unit (b) is preferably 1.5 to 19 mass%, more preferably 2 to 18 mass%, and even more preferably 3 to 17 mass% with respect to 100 mass% of the total mass of the vinyl chloride-based copolymer from the viewpoint of better achievement of the desired effect of the present invention.
In the present invention, when the content of the structural unit (c) is more than 60 mass%, the copolymerization reaction for obtaining the copolymer is difficult; when the content of the structural unit (c) is 19 mass% or less, the self-plasticization property of the resulting vinyl chloride-based copolymer is deteriorated, and the mechanical properties (for example, elongation at break and the like) do not satisfy the requirements of the application field of the soft vinyl chloride-based resin. In some preferred embodiments, the content of the structural unit (c) is preferably 22 to 55 mass%, more preferably 25 to 50 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer, from the viewpoint of better achieving the desired effect of the present invention.
In the present invention, in some preferred embodiments, the content of the structural unit (a) is preferably 40 to 79.5 mass%, more preferably 45 to 75 mass%, and still more preferably 50 to 72 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer. When the content of the structural unit (a) is more than the above preferred range, the mechanical properties of the resulting vinyl chloride-based copolymer tend not to satisfy the requirements of the mechanical properties (e.g., elongation at break, etc.) of the soft vinyl chloride-based resin. When the content of the structural unit (a) is less than the above preferred range, the mechanical properties of the resulting vinyl chloride-based copolymer tend to deteriorate and the copolymerization reaction for obtaining the copolymer tends to be difficult.
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 ranges with respect to 100 mass% of the total mass of the vinyl chloride-based copolymer.
From the viewpoint of better improving the self-plasticization, processability, transparency and mechanical properties of the vinyl chloride-based copolymer and better adapting the vinyl chloride-based copolymer of the present invention to the application field of soft PVC, the total content of the structural unit (b) and the structural unit (c) is preferably more than 20 mass% and 60 mass% or less, more preferably 25 to 56 mass%, still more preferably 30 to 52 mass% relative to 100 mass% of the total mass of the soft vinyl chloride-based copolymer.
In other preferred embodiments, the mass ratio of the structural unit (b) to the structural unit (c) in the soft vinyl chloride-based copolymer is preferably 1/40 to 1/1, more preferably 1/35 to 1/2, still more preferably 1/25 to 1/5, from the viewpoint of more balanced balance of water resistance, transparency, plasticization, processability and mechanical properties.
(structural units based on other monomers)
The soft vinyl chloride-based copolymer of the present invention may include structural units based on other monomers 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 effect 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 the other monomer include, but are not limited to, a structural unit based on a vinyl ether-based monomer, 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, 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 needed.
In the present invention, it is preferable that the soft vinyl chloride-based copolymer of the present invention does not include a structural unit based on a polyalkylene glycol alkyl ether (meth) acrylate-based monomer, for example, a structural unit (b) included in the vinyl chloride-based copolymer described in patent document 1.
Structural unit based on vinyl ether monomer
The structural unit based on the vinyl ether monomer is a structural unit based on a monomer represented by the following formula (3).
CH 2 ＝CHOR 6 (3)
In the formula (3), R 6 Selected 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 such as chlorine, bromine, fluorine, or the like. Preferably, R 6 Selected from the group consisting of 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, which may be substituted with a halogen atom such as chlorine, bromine, fluorine, or the like. In addition, the hydrogen atom in formula (3) (meaning "CH" in formula (3)) 2 =hydrogen atom in CH- ") may also be substituted with a halogen atom such as chlorine, bromine, fluorine, or the like.
Examples of the monomer represented by the above formula (3) 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 preferable. These monomers may be used alone or in combination of two or more.
When the soft vinyl chloride-based copolymer of the present invention has a structural unit based on the monomer of the above formula (3), it is possible to provide more excellent self-plasticization and also more excellent biocompatibility and lubricity.
Structural unit 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 (4).
CH 2 ＝CR 4 COOR 7 (4)
In the formula (4), R 4 R is as defined above 7 Selected from the group consisting of 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, preferably selected from the group consisting of 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. In addition, the hydrogen atom in formula (4) (meaning "CH" in formula (4)) 2 Hydrogen atom in= "or the like) may be substituted with a halogen atom such as chlorine, bromine, fluorine, or the like.
Examples of the monomer represented by the above formula (4) 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, trideoxyfluoride (meth) acrylate. Of these, 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 soft vinyl chloride-based copolymer of the present invention has a structural unit based on the monomer of the above formula (4), excellent processing lubricity (e.g., reduced adhesion to twin rolls or screws, reduced melt viscosity, etc.) and antibacterial/antifouling properties of the product can be provided.
Structural unit based on maleimide monomer
Examples of the maleimide-based monomer forming the structural unit based on the maleimide-based monomer include, but are not limited to, 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 unit based on acrylonitrile monomer
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.
Structural units based on monomers containing carboxyl groups
Examples of the carboxyl group-containing monomers forming the structural unit based on the carboxyl group-containing monomer include, but are not limited to, 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-based copolymer of the present invention can represent the structure of the copolymer, and is used for expressing the self-plasticity of the copolymer.
From the viewpoint of achieving both of more excellent self-plasticization and processability, the vinyl chloride-based copolymer of the present invention preferably has only one glass transition temperature. Further, the glass transition temperature is not particularly limited in general, as long as it is lower than that of homopolymerized polyvinyl chloride. However, the glass transition temperature is preferably below 60 ℃, more preferably below 55 ℃. 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 invention tends to deteriorate.
In the present invention, the glass transition temperature can be measured by a dynamic thermo-mechanical analyzer (DMTA).
(number average molecular weight)
The number average molecular weight of the vinyl chloride-based 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 even more preferably 60000 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 be lowered. When the number average molecular weight is more than the above range, the polymerization temperature required tends to be too low, resulting in low conversion and increased production cost.
In the present invention, the number average molecular weight can be determined by Gel Permeation Chromatography (GPC) with polystyrene as a standard.
(physical Properties)
As is generally understood in the art, polyvinyl chloride generally needs to be processed with an additional plasticizer, and thus, polyvinyl chloride resins are classified into rigid polyvinyl chloride (e.g., plasticizer content of less than 20%) and flexible polyvinyl chloride (e.g., plasticizer content of 20% or more) and the like according to the content of the additional plasticizer therein, and exhibit differences in physical properties such as mechanical properties. However, since the vinyl chloride-based copolymer of the present invention is a new copolymer different from polyvinyl chloride and can be plasticized excellently even without adding a plasticizer, it is judged in the present invention whether the polyvinyl chloride-based copolymer satisfies the requirements in the art for soft PVC mainly based on the range of tensile elongation at break. Specifically, in the present invention, the tensile elongation at break of the vinyl chloride-based copolymer is preferably more than 140%, preferably more than 160%, more preferably more than 180%, still more preferably more than 200%, particularly preferably more than 220% according to the test method of GB/T1040-2006.
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/T1040-2006.
In the present invention, the hardness of the vinyl chloride-based copolymer is preferably 50 to 100 according to GB/T2411-2008 test method (Shore A).
In the present invention, the light transmittance of the vinyl chloride-based copolymer is preferably more than 75%, more preferably more than 78%. Typically, light transmittance is measured by methods known in the art using an ultraviolet-visible spectrophotometer.
It is particularly preferable that the soft vinyl chloride-based copolymer of the present invention satisfies all of the above physical properties simultaneously.
< method for producing Soft vinyl chloride copolymer >
The method for producing a soft vinyl chloride-based copolymer of the present invention is a method for producing the soft vinyl chloride-based copolymer, comprising: the raw materials including vinyl chloride, the monomer represented by the above formula (1) and the monomer represented by the above formula (2) are subjected to copolymerization reaction.
Details of vinyl chloride, the monomer represented by formula (1), the monomer represented by formula (2), and other monomers have been described above, and are not described here.
Examples of the copolymerization reaction of the present invention include, but are not limited to, block polymerization, random polymerization, graft polymerization, gradient polymerization. Among them, random polymerization is preferable from the viewpoint of more advantageously exhibiting the technical effects of the present application, that is, the molecular chain of the soft vinyl chloride-based copolymer of the present invention preferably has a random structure. More preferably, the soft 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 soft vinyl chloride-based copolymer of the present invention can be obtained, and a general radical polymerization method, a living radical polymerization method, or the like can be employed. However, from the viewpoint of facilitating industrial production, the method for producing a soft vinyl chloride-based copolymer of the present invention is based on a general radical polymerization mechanism.
As the polymerization method, any polymerization method which can be carried out based on a radical polymerization mechanism, for example, emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, slurry polymerization, gas phase polymerization, interfacial polymerization, or the like can be employed. 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 included in a polymerization system, and is preferably carried out by polymerizing each monomer used in the present invention in the presence of an initiator.
When the bulk polymerization method is employed, the order and manner of addition of the monomers are not limited, and the monomers may be added together or in any combination in portions.
Specific examples of initiators suitable for the bulk polymerization process include, but are not limited to: azo-based initiators such as azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, and the like; organic peroxide initiators such as t-butyl peroxyneoheptanoate, t-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, di-hexadecyl dicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxypivalate, di- (4-t-butylcyclohexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-butyl peroxydicarbonate, di- (2-ethylhexyl) peroxydicarbonate, t-butyl peroxy2-ethylhexanoate, ditetradecyl peroxydicarbonate, t-butyl peroxyacetate, cumene peroxyneodecanoate, di-t-butyl peroxide, cyclohexylsulfonyl acetyl peroxide, dibenzoyl peroxide, 1, 3-tetramethylbutyl peroxyneodecanoate, di-3-methoxybutyl peroxydicarbonate, 1, 3-tetramethylbutyl peroxypivalate, and the like. These radical initiators may be used alone or in combination of two or more. In particular, radical initiators having decomposition temperatures 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.
In addition, in the copolymerization of the present invention, a molecular weight regulator may be optionally added according to a desired molecular weight range, and specific examples of molecular weight regulators suitable for addition include, but are not limited to: n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, mercaptoacetic acid, trichloropropene, etc., preferably mercaptoethanol, n-dodecyl mercaptan, etc.
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 method of the present invention is a suspension polymerization method known in the art. Preferably, the suspension polymerization method of the present invention is carried out in a state where stirring 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, but are not limited to: alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, and the like; ketones such as acetone, butanone, cyclohexanone, and the like; 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.
From the viewpoint of easy recovery, the dispersion medium is preferably water. As for water, various forms of tap water, deionized water, distilled water, and the like can be employed.
The dispersant in the suspension polymerization method may be a dispersant known in the art, such as an anionic dispersant, a cationic dispersant, a nonionic dispersant, a polymeric dispersant.
Specific examples of the dispersant may include, but are not limited to: water-soluble organic high molecular substances, for example, partially hydrolyzed polyvinyl alcohol, polyvinyl pyrrolidone, salts of polyacrylic acid or polymethacrylic acid, such as maleic anhydride/styrene copolymer, and the like, synthetic high molecules, such as methylcellulose, hydroxymethyl cellulose, hydroxypropyl methylcellulose and other cellulose derivatives, such as gelatin, proteins, starch, sodium alginate and other natural high molecules; and water insoluble inorganic powders, for example, magnesium carbonate, calcium carbonate, barium sulfate, calcium phosphate, talc, kaolin; etc. These dispersants may be used singly or in combination of two or more. In view of the product particle size, shape, transparency of the resin and film forming property, a water-soluble organic polymer substance is preferably used, and a mixture of polyvinyl alcohol and a cellulose derivative is more preferably used. The amount of the dispersant to be 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 mass%, more preferably 15 to 50 mass%, relative to the total mass of the dispersion medium.
When the suspension polymerization method is employed, the order and manner of addition of the monomers are not limited, and the monomers may be added together or in any combination in portions.
The types of molecular weight regulators, the types of initiators, the amounts of initiators and the polymerization conditions (polymerization temperature, polymerization time, etc.) suitable for the suspension polymerization are the same as those in the above "(bulk polymerization), and are not described in detail herein.
(emulsion polymerization method)
The emulsion polymerization process of the present invention is an emulsion polymerization process well known in the art. Preferably, the emulsion polymerization process of the present invention is carried out in a state where stirring is applied to the polymerization system.
The kind of the dispersion medium is the same as that in the above "(suspension polymerization method)", and a description thereof will not be repeated here.
The monomer concentration in the system is preferably 5 to 60 mass%, more preferably 10 to 40 mass%, relative to 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 alkylphenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene styrenated phenyl ether, polyoxyalkylene benzylated phenyl ether, polyoxyalkylene cumyl phenyl ether, fatty acid polyglycol ether, polyoxyalkylene sorbitan fatty acid ester, and the like; anionic emulsifiers such as fatty acid soaps, rosin acid soaps, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfate salts, alkyl sulfosuccinates, and sulfate salts, phosphate salts, ether carboxylates, sulfosuccinates, and the like of nonionic emulsifiers having polyoxyalkylene chains; cationic emulsifiers, for example, stearyl trimethylammonium salt, cetyl trimethylammonium salt, lauryl trimethylammonium salt, dialkyl dimethylammonium salt, alkyl dimethylbenzyl ammonium salt, alkyl dimethylhydroxyethyl ammonium salt, and the like.
The amount of the emulsifier to be used is preferably 0.5 to 15 mass%, more preferably 1.0 to 10 mass%, based on 100 mass parts of the dispersion medium.
In addition, the emulsion polymerization method of the present invention may not use an emulsifier, that is, the emulsion polymerization method of the present invention may be based on a self-emulsion polymerization method.
In the case of emulsion polymerization, the order and mode of addition of the monomers are not limited, and the monomers may be added together or in any combination in portions.
Specific examples of initiators suitable for use in the emulsion polymerization process include, but are not limited to: an initiator as described in the above "(bulk polymerization)"; 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 types of molecular weight regulators suitable for use in the emulsion polymerization are the same as those in the above "(bulk polymerization method)", and will not be described here.
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-based resin composition of the present invention comprises the soft vinyl chloride-based copolymer.
The vinyl chloride-based resin composition of the present invention may optionally include other components in addition to the soft vinyl chloride-based copolymer of the present invention, examples of which include other resins such as other vinyl chloride-based resins, propylene-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, neoprene rubber, isoprene rubber, butadiene rubber, ethylene propylene diene rubber, and silicone rubber; thermoplastic elastomers such as olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, fluoropolymer-based thermoplastic elastomer, and the like. 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, further preferably 10 parts by mass or less, and particularly preferably 0 part by mass, based on 100 parts by mass of the vinyl chloride 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, matting agents, surfactants, leveling agents, surface-modifying agents, deaerating agents, heat stabilizers, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, antibacterial agents, foaming agents, crosslinking agents, lubricants, processing aids (e.g., ACR, etc.), and the like, in any amounts. 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 contain a plasticizer because the vinyl chloride-based copolymer of the present invention has excellent self-plasticization. In other preferred embodiments, since the vinyl chloride-based copolymer of the present invention has excellent processability, the vinyl chloride-based resin composition of the present invention does not contain a processing aid for improving processability.
The vinyl chloride-based resin composition of the present invention can be prepared by a method generally known in the art. For example, 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 twin roll mixer. The manner of preparation of the composition is not particularly limited, and the above-mentioned mixing may be performed in a single-stage or multi-stage manner depending on the desired composition of the composition. The mixing temperature and mixing speed of the above-mentioned mixing are also not particularly limited, and may be appropriately selected according to the desired composition of the composition.
< resin article >
The resin product of the present invention is a soft PVC molded product made of the 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 containers, PVC packaging films, PVC hoses, PVC cable wires, children's toys, and the like.
In some preferred embodiments, the resin article of the present invention may be a product used in the medical field, such as a transfusion tube, a blood transfusion bag, a medical catheter, a dialysis tube, a dialysis bag, a surgical glove, an artificial organ, or the like.
< example >
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
< evaluation method >
The composition ratio of each structural unit of the soft vinyl chloride-based copolymer, the number average molecular weight and molecular weight distribution (PDI) of the copolymer, the mechanical properties, the processability, the self-plasticizing property, the migration resistance, the biological properties and the transparency were evaluated by the following methods.
(copolymer composition ratio)
The copolymer composition ratio was determined by a Bruce AV400 nuclear magnetic resonance apparatus (THF-d 8 as 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 a Waters-1515 gel chromatograph with THF as eluent and polystyrene as standard.
(mechanical Properties)
100 parts of a vinyl chloride copolymer (or polyvinyl chloride in reference example) and 2 parts of a methyl tin mercaptide heat stabilizer were kneaded by a twin roll kneader, and then subjected to hot pressing at 175℃for 5 minutes and cold pressing for 5 minutes to obtain a sample. The obtained sample piece was cut into dumbbell-shaped sample pieces, and the tensile strength and elongation at break were measured according to GB/T1040-2006.
(workability)
Processability was evaluated by a torque rheometer. Specifically, 100 parts of a vinyl chloride-based copolymer (or polyvinyl chloride in reference example) was uniformly mixed with 2 parts of a methyl tin mercaptide heat stabilizer, and then tested in a Brabender internal mixer under the conditions of 175℃for 10 minutes. Processability was evaluated with a balance torque.
The degree of decrease in the equilibrium torque of the vinyl chloride-based copolymer obtained in each of the examples and comparative examples relative to the equilibrium torque of the homo-polyvinyl chloride obtained in the reference example was calculated by the following formula (1).
Formula (1): degree of decrease= (equilibrium torque of homo-polyvinyl chloride-equilibrium torque of vinyl chloride copolymer)/(equilibrium torque of homo-polyvinyl chloride) ×100%.
In the present invention, the degree of decrease is defined as 0 to 10% as a difference, the degree of decrease is defined as more than 10% and not more than 20% as a good, the degree of decrease is defined as more than 20% and not more than 30% as a good, and the degree of decrease is defined as more than 30% as a good.
(self plasticization)
Self plasticization was evaluated by glass transition temperature (Tg). The sample wafer was prepared in the same manner as in the evaluation of the mechanical properties described above. The sample piece obtained was cut into strips 5mm wide and 75mm long, and the glass transition temperature was measured by DMTA 2980 in a tensile mode at a test condition frequency of 1Hz and a temperature range of-60℃to 150 ℃.
(resistance to migration)
In the present invention, the evaluation of the migration resistance is whether or not a substance which is easily removed due to the introduction of a plasticizing segment into a molecular chain is present in the vinyl chloride-based copolymer.
The sample wafer was prepared in the same manner as in the evaluation of the mechanical properties described above. Each coupon was then cut in parallel into 2 groups of 5 patches each, weighed and recorded. Immersing the 2 groups of sample blocks in ethanol and water respectively, immersing for 48 hours at normal temperature, finally taking out, drying for 24 hours in a drying oven at 50 ℃, and weighing. The percentage of the mass difference before and after soaking (in ethanol or water) of the sample block to the mass of the sample block before soaking was calculated, and the average of the percentages was defined as the migration rate. It should be noted that the mobility should be less than or equal to 0.1%.
(biological property)
The sample wafer was prepared in the same manner as in the evaluation of the mechanical properties described above. Sample wafers were tested for hemolysis and cytotoxicity according to GB/T16886.5 and GB/T16886.12.
It should be noted that the value of the hemolysis ratio in GB/T16886.5 and GB/T16886.12 requires R <5%. In the invention, R is more than or equal to 5% as a difference, R is more than or equal to 2.5% and less than or equal to 2.5% as a good, R is more than or equal to 0.5% and less than or equal to 2.5% as a good, and R is more than or equal to 0.5% as a good.
(transparency)
The sample wafer was prepared in the same manner as in the evaluation of the mechanical properties described above. The light transmittance in the wavelength range of 500-800 nm is measured by an ultraviolet-visible spectrophotometer. In the present invention, the light transmittance is defined as being 75% or less, the light transmittance is defined as being more than 75% and 78% or less, the light transmittance is defined as being more than 78% and 82% or less, the light transmittance is defined as being more than 82%, and the light transmittance is defined as being most preferable.
Example 1 ]
Into a stainless steel reaction vessel having a volume of 500ml, 200g of deionized water, 20.8g of a 2 mass% PVA aqueous solution, 0.149g of Azobisisobutyronitrile (AIBN) as an initiator, 5.4g of vinyl 2-ethylhexanoate (V2 EH), 21.6g of isooctyl acrylate (EHA) were charged, and the air in the reaction vessel was replaced by charging nitrogen for 5 minutes. 81g of Vinyl Chloride (VC) monomer was then introduced into the reactor. After 30min of pre-stirring, the temperature is raised to 65 ℃ to start polymerization, and the addition mass ratio VC of the monomers is expressed as V2EH: EHA=75:5:20, and the polymerization reaction time is 8 hours. After the polymerization was completed, unreacted VC monomer was recovered, and the polymerization product was alternately washed with a large amount of deionized water and ethanol to obtain 98.6g of a vinyl chloride-based copolymer as white solid particles, the composition of the obtained resin was: the content of the structural unit (a) was 73.8 mass%, the content of the structural unit (b) was 4.4 mass%, and the content of the structural unit (c) was 21.8 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 2 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=70:10:20, the composition of the obtained resin was: the content of the structural unit (a) was 68.7 mass%, the content of the structural unit (b) was 9.8 mass%, and the content of the structural unit (c) was 21.5 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 3 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=70:5:25, the composition of the obtained resin was: the content of the structural unit (a) was 68.7 mass%, the content of the structural unit (b) was 4.6 mass%, and the content of the structural unit (c) was 26.7 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 4 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=70:2:28, the composition of the obtained resin was: the content of the structural unit (a) was 68.8 mass%, the content of the structural unit (b) was 1.9 mass%, and the content of the structural unit (c) was 29.3 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 5 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=70:1.5:28.5, the composition of the obtained resin was: the content of the structural unit (a) was 69.1 mass%, the content of the structural unit (b) was 1.1 mass%, and the content of the structural unit (c) was 29.8 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 6 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=65:5:30, the composition of the obtained resin was: the content of the structural unit (a) was 63.6 mass%, the content of the structural unit (b) was 4.2 mass%, and the content of the structural unit (c) was 32.2 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 7 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=55:5:40, the composition of the obtained resin was: the content of the structural unit (a) was 52.6 mass%, the content of the structural unit (b) was 4.4 mass%, and the content of the structural unit (c) was 43 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 8 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=50:15:35, the composition of the obtained resin was: the content of the structural unit (a) was 48.2 mass%, the content of the structural unit (b) was 14.1 mass%, and the content of the structural unit (c) was 37.7 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 9 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=50:18:32, the composition of the obtained resin was: the content of the structural unit (a) was 48.5 mass%, the content of the structural unit (b) was 17.5 mass%, and the content of the structural unit (c) was 34 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 10 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1 except that V2EH was replaced with the monomer represented by the formula (1-5), and the resulting resin had the following composition: the content of the structural unit (a) was 73.5 mass%, the content of the structural unit (b) was 4.2 mass%, and the content of the structural unit (c) was 22.3 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 11 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1 except that V2EH was replaced with vinyl 2, 2-dimethylhexanoate, and the resulting resin had the following composition: the content of the structural unit (a) was 72.9 mass%, the content of the structural unit (b) was 4.5 mass%, and the content of the structural unit (c) was 22.6 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 12 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1 except that V2EH was replaced with vinyl pivalate (monomer represented by formula (1-1)), and the resulting resin had a composition of: the content of the structural unit (a) was 73.0 mass%, the content of the structural unit (b) was 4.1 mass%, and the content of the structural unit (c) was 22.9 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 13 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1 except that V2EH was replaced with vinyl 2-methylheptanoate, and the resulting resin had the following composition: the content of the structural unit (a) was 73.0 mass%, the content of the structural unit (b) was 4.4 mass%, and the content of the structural unit (c) was 22.6 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 14 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1 except that V2EH was replaced with vinyl 2-methylpropionate, and the resulting resin had the following composition: the content of the structural unit (a) was 72.4 mass%, the content of the structural unit (b) was 4.0 mass%, and the content of the structural unit (c) was 23.6 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Example 15 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1 except that EHA was replaced with Butyl Acrylate (BA), and the resulting resin had the following composition: the content of the structural unit (a) was 72.6 mass%, the content of the structural unit (b) was 3.9 mass%, and the content of the structural unit (c) was 23.5 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 1 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1, except that V2EH was not used, the monomer charge mass ratio VC: eha=75:25, and the composition of the obtained resin was: the content of the structural unit (a) was 72.6 mass% and the content of the structural unit (c) was 27.4 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 2 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1, except that no EHA was used, and the monomer charge mass ratio VC: v2eh=75:25, the composition of the obtained resin was: the content of the structural unit (a) was 75.7 mass% and the content of the structural unit (b) was 24.3 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 3 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=75:10:15, the composition of the obtained resin was: the content of the structural unit (a) was 73.7 mass%, the content of the structural unit (b) was 9.5 mass%, and the content of the structural unit (c) was 16.8 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 4 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=55:25:20, the composition of the obtained resin was: the content of the structural unit (a) was 53.7 mass%, the content of the structural unit (b) was 23.7 mass%, and the content of the structural unit (c) was 22.6 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 5 ]
The polymerization and post-treatment were carried out using the same procedure as in example 1, with the proviso that the monomer feed mass ratio VC: V2EH: eha=30:5:65, the composition of the obtained resin was: the content of the structural unit (a) was 28 mass%, the content of the structural unit (b) was 4.5 mass%, and the content of the structural unit (c) was 67.5 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 6 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1, except that E2HA was replaced with vinyl acetate (VAc). The composition of the obtained resin is as follows: the content of the structural unit (a) was 73.5 mass%, the content of the structural unit (b) was 5.1 mass%, and the content of the structural unit (c) was 21.4 mass%, relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
Comparative example 7 ]
Polymerization and post-treatment were carried out by the same procedure as in example 1, except that E2HA was replaced with vinyl n-octoate. The composition of the obtained resin is as follows: the content of the structural unit (a) was 73.3 mass%, the content of the structural unit (b) was 4.6 mass%, and the content of the structural unit (c) was 22.1 mass% relative to 100 mass% of the total mass of the vinyl chloride-based copolymer.
< reference example >
The polymerization and post-treatment were carried out by the same procedure as in example 1, except that only VC monomer was used as the polymerization monomer. In the reference example, homopolymerized polyvinyl chloride was obtained.
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Note that: in Table 3, in comparative examples 6 and 7, the amounts marked by "(b)" are the amount of structural units based on vinyl acetate and the amount of structural units based on vinyl n-octoate, respectively. In addition, regarding the shore a hardness, in comparative examples 2, 3 and reference example, the hardness of the obtained product exceeded the measurement range of the shore a hardness, and therefore "undetectable" was noted.
In comparative example 1, since the resin state, self-plasticity and transparency were not desirable, the processability, hemolysis and cytotoxicity were not evaluated. In comparative example 2, the mechanical properties did not meet the expectations for the soft resin, and therefore, the processability, hemolysis, and cytotoxicity were not evaluated.
In comparative examples 4 and 5, the copolymer resin had too low an in-process viscosity and severe sticking to the rolls, and was not suitable for practical use.
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (10)

1. A soft 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),
in the formula (1), R 1 Selected from hydrogen and alkyl groups having 1 to 6 carbon atoms; r is R 2 Selected from alkyl groups having 1 to 5 carbon atoms; each R is 3 Independently selected from hydrogen and alkyl groups of 1 to 22 carbon atoms, but not simultaneously hydrogen,
in the formula (2), R 4 Selected from hydrogen and methyl, R 5 Selected from alkyl groups having 1 to 18 carbon atoms and hydroxyalkyl groups having 1 to 18 carbon atomsA group, an alkoxyalkyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 18 carbon atoms, and a cycloalkyl group having 3 to 18 atoms and having a hetero atom;
the content of the structural unit (b) is 1 to 20 mass% and the content of the structural unit (c) is more than 19 mass% and 60 mass% or less relative to 100 mass% of the total mass of the soft vinyl chloride copolymer.
2. The soft vinyl chloride-based copolymer according to claim 1, wherein in the formula (1), R 1 Selected from hydrogen and methyl; r is R 2 Selected from alkyl groups having 1 to 4 carbon atoms; each R is 3 Independently selected from hydrogen and alkyl groups having 1 to 18 carbon atoms, but not simultaneously hydrogen.
3. The soft vinyl chloride-based copolymer according to claim 1 or 2, wherein in the formula (2), R 5 Selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 hetero atoms.
4. A soft vinyl chloride-based copolymer according to any one of claims 1 to 3, wherein the content of the structural unit (a) is 40 to 79.5 mass% relative to 100 mass% of the total mass of the soft vinyl chloride-based copolymer.
5. The soft vinyl chloride-based copolymer according to any one of claims 1 to 4, wherein the total content of the structural unit (b) and the structural unit (c) is more than 20% by mass and 60% by mass or less relative to 100% by mass of the total mass of the soft vinyl chloride-based copolymer.
6. The soft vinyl chloride-based copolymer according to any one of claims 1 to 5, wherein the mass ratio of the structural unit (b) to the structural unit (c) in the soft vinyl chloride-based copolymer is 1/40 to 1/1.
7. The soft vinyl chloride-based copolymer according to any one of claims 1 to 6, wherein the soft vinyl chloride-based copolymer has a tensile elongation at break of more than 140%; the number average molecular weight of the soft vinyl chloride copolymer is 40000-250000.
8. A method for producing the soft vinyl chloride-based copolymer according to any one of claims 1 to 7, comprising: copolymerizing a raw material comprising vinyl chloride, the monomer represented by the formula (1) and the monomer represented by the formula (2).
9. A vinyl chloride-based resin composition, characterized in that it comprises the soft vinyl chloride-based copolymer according to any one of claims 1 to 7.
10. A resin article, characterized in that it is made of the vinyl chloride-based resin composition according to claim 9.
CN202311795041.XA 2023-12-25 2023-12-25 Soft vinyl chloride copolymer, process for producing the same, vinyl chloride resin composition, and resin product Pending CN117820535A (en)

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