Plasticizer, method for producing same, vinyl chloride-based resin composition, and vinyl chloride-based resin molded article

Abstract

The present invention relates to a plasticizer, a method for preparing the same, a vinyl chloride resin composition, and a vinyl chloride resin molded article. The plasticizer according to the present invention includes a vinyl chloride-based polymer plasticizer including a vinyl chloride-based unit and a unit represented by formula (A): in formula (A), R1 is each independently hydrogen, a C1-20 alkyl group, or a C6-20 aryl group, R2 is hydrogen, a C1-8 alkyl group, or a C6-12 aryl group, Q is an organic group having a valence of n + 1, L is a group represented by formula (B), n is an integer of 1-5, and n is an integer of 1-5. In the formula (B), R3 is independently hydrogen or C1-12 alkyl, R4 is independently hydrogen or-C (= O) R5, R5 is C1-12 alkyl, p is an integer from 1 to 20, and q is an integer from 10 to 120.

Description

Technical Field

[0001] This invention relates to a plasticizer and its preparation method, a vinyl chloride-based resin composition, and a vinyl chloride-based resin molded article. Background Technology

[0002] Polyvinyl chloride (PVC) resin is widely used in a range of fields, from industrial and construction to biomedical materials, due to its excellent chemical resistance, chemical stability, thermoplasticity, and low manufacturing cost. However, due to the high dipole interaction between polymer chains, PVC itself is a rigid material at room temperature. Therefore, a large amount of plasticizer is often needed to improve the processability and toughness of PVC, making PVC products suitable for a wide range of applications. Among these, phthalate plasticizers, such as 2-ethylhexyl phthalate and di-n-butyl phthalate, are widely used.

[0003] Specifically, phthalate plasticizers possess highly efficient and excellent plasticizing properties. However, because these plasticizers lack chemical bonds with polyvinyl chloride (PVC), they can migrate to the surface of PVC products. This not only leads to a decline in the performance of the products but also causes environmental pollution due to the migrating phthalate plasticizers. Furthermore, phthalate products have certain toxic side effects on the human body. Phthalate salts, in particular, have certain toxic side effects on the developmental and reproductive systems, leading to damage to the liver, kidneys, and lungs, as well as abnormal sexual development.

[0004] Therefore, additive polymeric plasticizers have attracted attention, with the expectation that they will be non-toxic. For example, polycaprolactone (PCL) is a non-toxic and harmless polymer currently used in blends with polyvinyl chloride (PVC) to lower the glass transition temperature of PVC blends. However, compared to PVC, PCL is more expensive, significantly increasing production costs. Furthermore, PCL, as a plasticizer, is still prone to precipitating from PVC products, which may affect the mechanical properties of these products. Simultaneously, due to the high crystallinity of PCL, the precipitated PCL can crystallize on the surface of PVC products, thus reducing their transparency.

[0005] In addition, for additive polymeric plasticizers, it is generally desirable to increase the chain length of the polymeric plasticizer to improve migration resistance, but this can sometimes impair plasticizing performance.

[0006] Therefore, it is sometimes desirable to incorporate polycaprolactone segments onto a polyvinyl chloride (PVC) resin matrix. However, from a polymerization mechanism perspective, vinyl chloride polymerization is a free radical polymerization mechanism, while caprolactone polymerization is a ring-opening polymerization mechanism. These different polymerization mechanisms increase the difficulty of preparing the relevant products. In response, Non-Patent Literature 1 describes the preparation of hydroxyl-terminated PVC using a reversible addition-fragmentation chain transfer polymerization method, followed by ring-opening polymerization of caprolactone using the hydroxyl-terminated PVC as a macromolecular initiator to obtain a vinyl chloride-caprolactone block copolymer. This technology employs a specific polymerization method, has very high requirements for the production process, and also requires the introduction of a large amount of polycaprolactone segments. Therefore, this type of technology is costly and essentially has no industrial application value.

[0007] <<Existing Technical Documents>>

[0008] Non-patent literature 1: ZHSun et al. Nonmigratory poly(vinyl chloride)-block-polycaprolactone plasticizers and compatibilizers prepared by sequential RAFTand ring-opening polymerization(RAFT-T-ROP). Macromolecules, 2019, 52(4):1746-1756. Summary of the Invention

[0009] <<The Problem the Invention Aims to Solve>>

[0010] To address the aforementioned deficiencies, the object of this invention is to provide an additive plasticizer comprising a vinyl chloride copolymer, which can be obtained easily and at low cost, and effectively plasticizes vinyl chloride resins, exhibiting excellent migration resistance in the prepared molded articles. Furthermore, the object of this invention is to provide a method for obtaining the aforementioned plasticizer easily and at low cost. Additionally, the object of this invention is to provide a vinyl chloride resin composition that produces molded articles with excellent plasticizing and migration resistance, and molded articles obtained therefrom.

[0011] <<Solutions for Problem Solving>>

[0012] According to the inventor's dedicated research, the above-mentioned technical problems can be solved by implementing the following technical solution:

[0013] [1]. A plasticizer comprising a vinyl chloride-based polymeric plasticizer, said vinyl chloride-based polymeric plasticizer comprising vinyl chloride-based units and units represented by the following formula (A):

[0014]

[0015] In formula (A), R1 is independently hydrogen, C1-20 alkyl or C6-20 aryl, R2 is hydrogen, C1-8 alkyl or C6-12 aryl, Q is an organic group with an n+1 valence, L is the group shown in formula (B) below, and n is an integer from 1 to 5.

[0016]

[0017] In formula (B), R3 is each independently hydrogen or a C1-12 alkyl group, R4 is each independently hydrogen or -C(=O)R5, where R5 is a C1-12 alkyl group, p is an integer from 1 to 20, and q is an integer from 10 to 120.

[0018] [2]. According to the plasticizer described in [1], in formula (A), R1 is each independently hydrogen, C1-10 alkyl or C6-10 aryl, R2 is hydrogen, C1-5 alkyl or C6-10 aryl, and n is an integer from 1 to 3;

[0019] In formula (B), R3 is hydrogen or a C1-10 alkyl group, R4 is hydrogen or -C(=O)R5, where R5 is a C1-10 alkyl group, p is an integer from 3 to 15, and q is an integer from 15 to 120.

[0020] [3]. The plasticizer according to [1] or [2], wherein Q is a group represented by formula (C) or a group represented by formula (D):

[0021]

[0022] In formulas (C) and (D), * represents the connection with -OL, and R6 and R7 are each independently an n+1 valence group obtained by removing n+1 hydrogen atoms from an alkane, an n+1 valence group having an ether oxygen atom at the end of the aforementioned n+1 valence group and / or between carbon-carbon bonds, or an n+1 valence group obtained by removing n+1 hydrogen atoms from an aromatic hydrocarbon. The definition of n is the same as the definition of n in formula (A).

[0023] [4]. The plasticizer according to any one of [1] to [3], wherein, relative to 100% by mass of the total mass of the vinyl chloride-based polymer plasticizer, the content of the vinyl chloride-based unit is 2 to 60% by mass, and the content of the unit shown in formula (A) is 35 to 95% by mass.

[0024] [5]. The plasticizer according to any one of [1] to [4], wherein,

[0025] The glass transition temperature of the vinyl chloride-based polymeric plasticizer is below 25°C; and / or

[0026] The number average molecular weight (Mn) of the vinyl chloride-based polymeric plasticizer is 10,000 to 50,000; and / or

[0027] The molecular weight distribution of the vinyl chloride-based polymeric plasticizer is 1.2 to 3.5.

[0028] [6]. The plasticizer according to any one of [1] to [5], wherein the vinyl chloride-based polymeric plasticizer is obtained based on a vinyl chloride-based copolymer precursor, the vinyl chloride-based copolymer precursor comprising vinyl chloride-based units and units represented by the following formula (A'):

[0029]

[0030] The definitions of R1, R2, Q, and n in equation (A') are the same as those in equation (A).

[0031] [7]. A method for preparing a plasticizer, comprising:

[0032] (1) Copolymerize vinyl chloride with the monomer shown in formula (a') to obtain a vinyl chloride copolymer precursor comprising vinyl chloride-based units and units shown in formula (A'):

[0033]

[0034] In formulas (a') and (A'), R1 is independently hydrogen, a C1-20 alkyl group or a C6-20 aryl group, R2 is hydrogen, a C1-8 alkyl group or a C6-12 aryl group, Q is an organic group with an n+1 valence, and n is an integer from 1 to 5;

[0035] (2) Using the vinyl chloride copolymer precursor as a macromolecular initiator, the lactone monomer shown in formula (b) is subjected to ring-opening polymerization to obtain a vinyl chloride polymeric plasticizer P1 comprising vinyl chloride-based units and units shown in formula (A1):

[0036]

[0037] In formula (b), R3 is each independently hydrogen or a C1-12 alkyl group, and p is an integer from 1 to 20.

[0038] In formula (A1), the definitions of R1, R2, Q, and n are the same as those in formula (A'), and L1 is the group shown in formula (B1).

[0039]

[0040] In equation (B1), the definitions of R3 and p are the same as those in equation (b). 41 For hydrogen, q is an integer from 10 to 120;

[0041] (3) Optionally, the vinyl chloride-based polymeric plasticizer P1 is reacted with an anhydride represented by formula (c) to obtain a vinyl chloride-based polymeric plasticizer P2 comprising vinyl chloride-based units and units represented by formula (A2).

[0042] R5(O=)COC(=O)R5 (c)

[0043] In formula (c), each of R5 is an alkyl group from C1 to C12.

[0044] In formula (A2), the definitions of R1, R2, Q, and n are the same as those in formula (A'), and L2 is the group shown in formula (B2).

[0045]

[0046] In equation (B2), the definitions of R3 and p are the same as those in equation (b). 42 Each is independently hydrogen or -C(=O)R5, but all R in the vinyl chloride-based polymeric plasticizer P2 42 Not all are hydrogen, and q is an integer from 10 to 120.

[0047] [8]. According to the preparation method described in [7], in step (1), the number-average molecular weight Mn of the vinyl chloride copolymer precursor is 5000 to 20000, and / or the molecular weight distribution of the vinyl chloride copolymer precursor is 1.2 to 3.5; and / or

[0048] In step (1), the content of the vinyl chloride-based unit is 50-95% by mass relative to 100% by mass of the total mass of the vinyl chloride copolymer precursor, and the content of the unit represented by formula (A') is 5-40% by mass; and / or

[0049] In step (1), the copolymerization temperature is 40–70°C, and the copolymerization time is 2–24 hours; and / or

[0050] In step (1), the copolymerization is carried out by suspension polymerization or precipitation polymerization.

[0051] [9]. According to the preparation method described in [7] or [8], in step (2), the feed ratio of the vinyl chloride copolymer precursor to the lactone monomer is converted to a molar ratio of hydroxyl groups in the vinyl chloride copolymer precursor to the lactone monomer of 1:10 to 1:120; and / or

[0052] In step (2), the polymerization temperature is -10 to 150°C, and the polymerization time is 1 to 24 hours; and / or

[0053] In step (2), the polymerization is carried out by solution polymerization.

[0054]

[10] . A vinyl chloride-based resin composition comprising:

[0055] Vinyl chloride resins, and

[0056] The plasticizer according to any one of [1] to [6], or the plasticizer obtained by any one of [7] to [9].

[0057]

[11] . A vinyl chloride resin molded article, said molded article being made by using the vinyl chloride resin composition according to claim 10.

[0058] <<The Effects of the Invention>>

[0059] By implementing the above technical solutions, the present invention can achieve the following technical effects:

[0060] The plasticizer incorporates vinyl chloride-based copolymers with units containing polylactone side chains (units shown in Formula (A)), which improves processing compatibility with and dispersibility in vinyl chloride resin matrices. Therefore, it exhibits excellent plasticizer properties during resin processing, and the resulting molded articles show excellent plasticizer migration resistance.

[0061] Furthermore, the plasticizer of the present invention can be easily obtained by methods commonly used in industry, thus significantly reducing production costs and making it particularly suitable for industrial applications. Detailed Implementation

[0062] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments.

[0063] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0064] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0065] In this specification, the numerical range referred to as "value A to value B" refers to the range including endpoint values ​​A and B. The numerical range referred to as "above" and "below" refers to the range including endpoint values. The numerical range referred to as "greater than" and "less than" refers to the range excluding endpoint values.

[0066] Unless otherwise specified, all "%" in this instruction manual refer to percentages by mass.

[0067] In this specification, the word "may" has two meanings: to perform a certain treatment or not to perform a certain treatment, or to have a certain component or not to have a certain component.

[0068] In this specification, "optional" or "optionally" means that the event or situation described below may or may not occur, and the description includes both the scenario in which the event occurs and the scenario in which the event does not occur.

[0069] In this specification, "alkane", "alkyl" or "alkylene" means unsubstituted "alkane", "alkyl" or "alkylene" in the form of a straight chain, branched chain or cyclic chain, and "aromatic", "aryl" or "arylene" means "aromatic", "aryl" or "arylene" in the form of an aromatic ring (benzene ring, naphthalene ring, etc.) without any substituents other than alkyl.

[0070] In this instruction manual, when "room temperature" or "room temperature" is used, the temperature can be between 10 and 40°C.

[0071] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to the described implementation that are included in at least one of the embodiments described herein, and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0072] <<Plasticizers>>

[0073] The plasticizers of the present invention include vinyl chloride-based polymeric plasticizers, wherein the vinyl chloride-based polymeric plasticizers comprise vinyl chloride-based units and units represented by the following formula (A):

[0074]

[0075] In formula (A), R1 is independently hydrogen, C1-20 alkyl or C6-20 aryl, R2 is hydrogen, C1-8 alkyl or C6-12 aryl, Q is an organic group with an n+1 valence, L is the group shown in formula (B) below, and n is an integer from 1 to 5.

[0076]

[0077] In formula (B), R3 is each independently hydrogen or a C1-12 alkyl group, R4 is each independently hydrogen or -C(=O)R5, where R5 is a C1-12 alkyl group, p is an integer from 1 to 20, and q is an integer from 10 to 120.

[0078] In some preferred embodiments, from the viewpoint of better migrating resistance, the content of the vinyl chloride-based polymeric plasticizer of the present invention in the plasticizer of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. In some more preferred embodiments, from the viewpoint of cost reduction, the plasticizer of the present invention is formed solely of the vinyl chloride-based polymeric plasticizer.

[0079] In this invention, there are no particular limitations on the form in which the plasticizer comprises a vinyl chloride-based polymeric plasticizer. For example, the plasticizer can be a vinyl chloride-based polymeric plasticizer itself, a mixture of a vinyl chloride-based polymeric plasticizer and other plasticizers, or a coated plasticizer in which a vinyl chloride-based polymeric plasticizer is contained within a coating material.

[0080] The details of the components that form the plasticizer of the present invention will be described in more detail below.

[0081] <Venecryl chloride-based polymeric plasticizers>

[0082] The vinyl chloride-based polymeric plasticizer of the present invention (hereinafter also referred to as polymeric plasticizer P) comprises a vinyl chloride-based unit and a unit shown in the following formula (A) (hereinafter also referred to as unit A):

[0083]

[0084] In formula (A), R1 is independently hydrogen, C1-20 alkyl or C6-20 aryl, R2 is hydrogen, C1-8 alkyl or C6-12 aryl, Q is an organic group with an n+1 valence, L is the group shown in formula (B) below, and n is an integer from 1 to 5.

[0085]

[0086] In formula (B), R3 is each independently hydrogen or a C1-12 alkyl group, R4 is each independently hydrogen or -C(=O)R5, where R5 is a C1-12 alkyl group, p is an integer from 1 to 20, and q is an integer from 10 to 120.

[0087] In some preferred embodiments, in formula (A), from the viewpoint of more readily obtaining vinyl chloride-based polymeric plasticizers, R1 is preferably each independently hydrogen, a C1-10 alkyl group, or a C6-10 aryl group, more preferably each independently hydrogen or a C1-5 alkyl group, and even more preferably each independently hydrogen or a C1-3 alkyl group. Each R1 may be the same or different.

[0088] In some preferred embodiments, in formula (A), from the viewpoint of more readily obtaining vinyl chloride-based polymeric plasticizers, R2 is preferably hydrogen, a C1-5 alkyl group or a C6-10 aryl group, more preferably hydrogen or a C1-3 alkyl group, and even more preferably hydrogen or methyl.

[0089] In some preferred embodiments, in formula (A), from the viewpoint of making it easier to obtain vinyl chloride-based polymeric plasticizers, n is preferably an integer from 1 to 3, more preferably 1 or 2.

[0090] In some preferred embodiments, in formula (B), R3 is preferably hydrogen or a C1-10 alkyl group. Each R3 may be the same or different.

[0091] In some preferred embodiments, in formula (B), R4 is each independently hydrogen or -C(=O)R5, wherein R5 is preferably a C1-10 alkyl group, more preferably a C1-6 alkyl group.

[0092] In some preferred embodiments, in formula (B), p is preferably an integer from 3 to 15, more preferably an integer from 3 to 10, and even more preferably an integer from 4 to 8.

[0093] In some preferred embodiments, in formula (B), from the viewpoint of better plasticizing while also taking into account the resistance to migration, q is preferably an integer from 15 to 120, and more preferably an integer from 20 to 100.

[0094] In this invention, there are no particular limitations on the group Q, as long as it can bind the side chain -OL to the main chain of the vinyl chloride-based polymeric plasticizer. In some preferred embodiments, from the viewpoint of more easily obtaining the vinyl chloride-based polymeric plasticizer of this invention, Q is preferably a group represented by formula (C) or formula (D):

[0095]

[0096] In formulas (C) and (D), * represents the connection point with -OL, and R6 and R7 are each independently an n+1 valence group obtained by removing n+1 hydrogen atoms from an alkane (hereinafter sometimes referred to as an n+1 valence alkane group), an n+1 valence group having an etheric oxygen atom at the end of the aforementioned n+1 valence group (i.e., an n+1 valence group obtained by removing n+1 hydrogen atoms from an alkane) and / or between carbon-carbon bonds (hereinafter sometimes referred to as an n+1 valence group with an etheric oxygen atom), or an n+1 valence group obtained by removing n+1 hydrogen atoms from an aromatic hydrocarbon (hereinafter sometimes referred to as an n+1 valence aromatic hydrocarbon group), the definition of n is the same as the definition of n in formula (A).

[0097] From the viewpoint of more easily obtaining the vinyl chloride-based polymeric plasticizer of the present invention, the n+1 valence alkane group is preferably an n+1 valence group obtained by removing n+1 hydrogen atoms from a C1 to 10 alkane, and more preferably an n+1 valence group obtained by removing n+1 hydrogen atoms from a C1 to 6 alkane. In the case of an n+1 valence alkane group, n is preferably an integer from 1 to 3, and more preferably 1 or 2.

[0098] From the viewpoint of more easily obtaining the vinyl chloride-based polymeric plasticizer of the present invention, as an n+1 valence group having an ether-type oxygen atom, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, as described above. Furthermore, the number of ether-type oxygen atoms is preferably 1 to 6, more preferably 2 to 4. Here, since the valence state of the n+1 valence alkane group is n+1, the number of ends of the n+1 valence alkane group is n+1. In this case, having an ether-type oxygen atom at the end of the aforementioned n+1 valence group means having an ether-type oxygen atom at at least one of the n+1 ends. In the case of an n+1 valence group having an ether-type oxygen atom, n is preferably 1 or 2, more preferably 1.

[0099] From the viewpoint of more easily obtaining the vinyl chloride-based polymeric plasticizer of the present invention, the n+1 valent aromatic group is preferably an n+1 valent group obtained by removing n+1 hydrogen atoms from an aromatic hydrocarbon of C6 to 10, and more preferably an n+1 valent group obtained by removing n+1 hydrogen atoms from an aromatic hydrocarbon of C6 to 8. In the case of an n+1 valent aromatic group, n is preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0100] In addition, alkanes and aromatics may each optionally have substituents (e.g., halogen, hydroxyl, carboxyl, cyano, nitrile, etc.) or not have substituents.

[0101] Specific examples of R6 and R7 include, but are not limited to: ethylene, propyleneene, butylene, pentylene, n-hexylene, cyclohexylene, trivalent propane group, trivalent butane group, and -(CH3O). x-(x is 1 to 20, preferably 2 to 20), -(C2H4O) x -(x is 1 to 20, preferably 2 to 20), -(C3H6O) x -(x is 1 to 20, preferably 2 to 20), phenylene, naphthylene, tolylene, trivalent phenyl group, tetravalent phenyl group, etc.

[0102] Furthermore, from the viewpoint of adjusting the properties of vinyl chloride-based polymeric plasticizers (e.g., compatibility with resin matrices, improvement of toughness or strength, etc.), the above-described vinyl chloride-based polymeric plasticizers of the present invention may optionally include other units. While not particularly limited, in some preferred embodiments, the other units may be at least one selected from units based on monofunctional (meth)acrylate monomers, units based on monofunctional vinyl ester monomers, units based on monofunctional vinyl ether monomers, and units based on monofunctional styrene monomers.

[0103] There are no particular limitations on monofunctional (meth)acrylate monomers, and examples include, but are not limited to: alkyl (meth)acrylates (preferably, alkyl (meth)acrylates having 1 to 8 alkyl carbon atoms), such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylates (preferably, hydroxyalkyl (meth)acrylates having 1 to 8 alkyl carbon atoms), such as methyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate; glycidyl (meth)acrylate, etc. These monofunctional (meth)acrylate monomers can be used alone or in any combination of two or more.

[0104] There are no particular limitations on monofunctional vinyl ester monomers, examples of which include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, etc. These monofunctional vinyl ester monomers can be used alone or in any combination of two or more.

[0105] There are no particular limitations on monofunctional vinyl ether monomers, and examples include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, etc. These monofunctional vinyl ether monomers can be used alone or in any combination of two or more.

[0106] There are no particular restrictions on monofunctional styrene monomers, and examples include, but are not limited to, styrene, α-methylstyrene, and o-methylstyrene. These monofunctional styrene monomers can be used alone or in any combination of two or more.

[0107] In this invention, there are no particular restrictions on the content of each unit in the vinyl chloride-based polymer plasticizer, and it can be adjusted appropriately as needed.

[0108] In some preferred embodiments, the content of vinyl chloride-based units is preferably 2 to 60% by mass, more preferably 5 to 55% by mass, and even more preferably 10 to 50% by mass, relative to 100% by mass of the total mass of the vinyl chloride-based polymeric plasticizer.

[0109] In some preferred embodiments, the content of the unit shown in formula (A) is preferably 35-95% by mass, more preferably 37-93% by mass, and even more preferably 40-90% by mass, relative to 100% by mass of the total mass of the vinyl chloride-based polymeric plasticizer.

[0110] In some preferred embodiments, the content of other units is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the total mass of the vinyl chloride-based polymeric plasticizer.

[0111] In addition, in some preferred embodiments, the content of other units in the vinyl chloride-based polymeric plasticizer is less than the content of vinyl chloride-based units.

[0112] In this invention, there are no particular limitations on the glass transition temperature (Tg) of the vinyl chloride-based polymeric plasticizer, as long as it can plasticize the resin matrix. In some preferred embodiments, the glass transition temperature of the vinyl chloride-based polymeric plasticizer is preferably below 25°C, more preferably below 10°C. The lower limit of the glass transition temperature is typically -10°C, for example -5°C.

[0113] In this invention, there is no particular limitation on the molecular weight of the vinyl chloride-based polymeric plasticizer. In some preferred embodiments, from the viewpoint of more easily balancing plasticizing effect and migration resistance, the number average molecular weight Mn of the vinyl chloride-based polymeric plasticizer is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, and even more preferably 20,000 to 40,000. In other preferred embodiments, from the same viewpoint, the molecular weight distribution of the vinyl chloride-based polymeric plasticizer is preferably 1.2 to 3.5, more preferably 1.4 to 2.4.

[0114] In this invention, the number-average molecular weight Mn and molecular weight distribution are determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0115] In this invention, there are no particular restrictions on the preparation method of vinyl chloride-based polymeric plasticizers, and any method known in the art can be used.

[0116] In some preferred embodiments, the vinyl chloride-based polymeric plasticizer is preferably obtained based on a vinyl chloride-based copolymer precursor, said precursor comprising vinyl chloride-based units and units represented by the following formula (A'):

[0117]

[0118] The definitions of R1, R2, Q, and n in equation (A') are the same as those in equation (A).

[0119] In some specific implementations, vinyl chloride-based polymeric plasticizers can be obtained by ring-opening polymerization of lactone compounds initiated from the aforementioned vinyl chloride copolymer precursors.

[0120] In some more specific embodiments, the vinyl chloride-based polymeric plasticizer is obtained by the <<Preparation Method of Plasticizer>> described later in this invention.

[0121] <Other Components>

[0122] As described above, the plasticizer of the present invention may optionally contain other components. Examples of other components include, but are not limited to, other plasticizers, coating materials, etc.

[0123] <<Preparation Methods of Plasticizers>>

[0124] The method for preparing the plasticizer of the present invention includes at least the step of preparing a vinyl chloride-based polymeric plasticizer (hereinafter also referred to as polymeric plasticizer P), said step including:

[0125] (1) Copolymerize vinyl chloride with the monomer shown in formula (a') to obtain a vinyl chloride copolymer precursor (hereinafter sometimes referred to as copolymer precursor F) comprising vinyl chloride-based units and units shown in formula (A') (hereinafter sometimes simply referred to as unit A'):

[0126]

[0127] In formulas (a') and (A'), R1 is independently hydrogen, a C1-20 alkyl group or a C6-20 aryl group, R2 is hydrogen, a C1-8 alkyl group or a C6-12 aryl group, Q is an organic group with an n+1 valence, and n is an integer from 1 to 5;

[0128] (2) Using the vinyl chloride copolymer precursor as a macromolecular initiator, the lactone monomer shown in formula (b) is subjected to ring-opening polymerization to obtain a vinyl chloride polymeric plasticizer P1 comprising vinyl chloride-based units and units shown in formula (A1) (hereinafter sometimes simply referred to as unit A1):

[0129]

[0130] In formula (b), R3 is each independently hydrogen or a C1-12 alkyl group, and p is an integer from 1 to 20.

[0131] In formula (A1), the definitions of R1, R2, Q, and n are the same as those in formula (A'), and L1 is the group shown in formula (B1).

[0132]

[0133] In equation (B1), the definitions of R3 and p are the same as those in equation (b). 41 For hydrogen, q is an integer from 10 to 120;

[0134] (3) Optionally, the vinyl chloride-based polymeric plasticizer P1 is reacted with an anhydride represented by formula (c) below to obtain a vinyl chloride-based polymeric plasticizer P2 comprising vinyl chloride-based units and units represented by formula (A2) below (hereinafter sometimes simply referred to as unit A2).

[0135] R5(O=)COC(=O)R5 (c)

[0136] In formula (c), each of R5 is an alkyl group from C1 to C12.

[0137] In formula (A2), the definitions of R1, R2, Q, and n are the same as those in formula (A'), and L2 is the group shown in formula (B2).

[0138]

[0139] In equation (B2), the definitions of R3 and p are the same as those in equation (b). 42 Each is independently hydrogen or -C(=O)R5, but all R in the vinyl chloride-based polymeric plasticizer P2 42 Not all are hydrogen, and q is an integer from 10 to 120.

[0140] The following will describe each process and step in detail. In addition, it should be noted that both vinyl chloride-based polymer plasticizer P1 and vinyl chloride-based polymer plasticizer P2 are copolymers P that can be used as vinyl chloride-based polymer plasticizers. Therefore, step (3) is a non-essential step that can be performed as needed or not.

[0141] <Step (1)>

[0142] In step (1), vinyl chloride is copolymerized with the monomer shown in formula (a') to obtain a vinyl chloride copolymer precursor comprising vinyl chloride-based units and units shown in formula (A'):

[0143]

[0144] In equations (a') and (A'), the details of R1, R2, Q and n are the same as those of R1, R2, Q and n in the aforementioned equation (A), and will not be repeated here.

[0145] When Q is a group represented by formula (C) above, examples of the monomers represented by (a') include, but are not limited to, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dihydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-hydroxyhexyl methacrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl methacrylate, hydroxyphenyl methacrylate, dihydroxyphenyl methacrylate, trihydroxyphenyl methacrylate, etc.

[0146] When Q is the group shown in formula (D) above, examples of the monomer shown in (a') include, but are not limited to, diethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxypropyl vinyl ether, etc.

[0147] Furthermore, from the viewpoint of adjusting the properties of the obtained vinyl chloride-based polymeric plasticizer (e.g., compatibility with the resin matrix, improvement of toughness or strength, etc.), other monomers can also be used to participate in the above copolymerization. In some preferred embodiments, the other monomers are at least one selected from monofunctional (meth)acrylate monomers, monofunctional vinyl ester monomers, monofunctional vinyl ether monomers, and monofunctional styrene monomers. Non-limiting examples of these monomers have been described above and will not be repeated here.

[0148] In this invention, there are no particular restrictions on the content of each unit in the vinyl chloride copolymer precursor, and it can be adjusted appropriately as needed.

[0149] In some preferred embodiments, the content of vinyl chloride-based units is preferably 50-95% by mass, more preferably 60-90% by mass, and even more preferably 65-90% by mass, relative to 100% by mass of the total mass of the vinyl chloride copolymer precursor.

[0150] In some preferred embodiments, the content of the unit represented by formula (A') is preferably 5 to 40% by mass, more preferably 6 to 30% by mass, and even more preferably 7 to 25% by mass, relative to 100% by mass of the total mass of the vinyl chloride copolymer precursor.

[0151] In some preferred embodiments, the content of units based on other monomers (also referred to as other units) is preferably less than 40% by mass, more preferably less than 15% by mass, and even more preferably less than 10% by mass, relative to 100% by mass of the total mass of the vinyl chloride copolymer precursor.

[0152] In this invention, there is no particular limitation on the molecular weight of the vinyl chloride copolymer precursor. In some preferred embodiments, from the viewpoint of more easily obtaining the desired vinyl chloride polymeric plasticizer, the number-average molecular weight Mn of the vinyl chloride copolymer precursor is 5000–20000, more preferably 7000–20000, and even more preferably 7000–15000. In other preferred embodiments, from the same viewpoint, the molecular weight distribution of the vinyl chloride copolymer precursor is preferably 1.2–3.5, more preferably 1.5–2.2.

[0153] In this invention, the number-average molecular weight Mn and molecular weight distribution are determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0154] In this invention, there are no particular restrictions on the amount of vinyl chloride, the monomer shown in formula (a'), and other optional monomers fed, as long as the desired copolymer precursor can be obtained.

[0155] In some preferred embodiments, the amount of vinyl chloride fed is preferably 60-98% by mass, more preferably 70-95% by mass, and even more preferably 80-95% by mass, relative to 100% by mass of all monomers.

[0156] In some preferred embodiments, the amount of monomer shown in formula (a') fed relative to 100% of the total mass of all monomers is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

[0157] In some preferred embodiments, the amount of other monomers fed is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the total mass of all monomers.

[0158] During copolymerization, various initiators known in the art can be added to the copolymerization system according to the polymerization method used. The amount of initiator can be 0.1–5% by mass, for example, 0.5–3% by mass, relative to 100% of the total mass of all monomers.

[0159] In addition, other auxiliaries, such as chain transfer agents, can be added to the copolymerization system during copolymerization. In some preferred embodiments, in the case of precipitation polymerization described later, surfactants such as dispersants and chain transfer agents are preferably not used.

[0160] In this invention, there are no particular limitations on the copolymerization conditions, which can be appropriately adjusted according to the polymerization method, monomer type, etc. In some specific embodiments, the copolymerization temperature can be 40–70°C, for example, 45–68°C. In other specific embodiments, the copolymerization time can be 2–24 hours, for example, 4–16 hours.

[0161] In this invention, there are no particular limitations on the polymerization method for copolymerization, such as emulsion polymerization, suspension polymerization, solution polymerization, precipitation polymerization, etc. Each polymerization method in this invention can be implemented using means known in the art.

[0162] In some preferred embodiments, from the viewpoint of more easily obtaining the desired vinyl chloride-based polymeric plasticizer, copolymerization is preferably carried out by suspension polymerization or precipitation polymerization, and more preferably by precipitation polymerization.

[0163] In the case of precipitation polymerization, for example, precipitation polymerization can be carried out by adding vinyl chloride, the monomer shown in formula (a') and optional other monomers to a solvent (the solvent that can dissolve the monomers but not the resulting copolymer) and polymerizing to obtain a spherical or near-spherical copolymer as a precipitate.

[0164] Furthermore, there are no particular restrictions on the specific type of solvent used in precipitation polymerization. Additionally, the molecular weight of the resulting copolymer can be adjusted by changing the type of solvent.

[0165] In precipitation polymerization, all monomers can be added at once, or various monomers can be added in batches.

[0166] In some specific embodiments, the total concentration of all monomers in the solvent is preferably 10-30% by mass, more preferably 12-28% by mass, and even more preferably 15-26% by mass. When the total monomer concentration is below the lower limit, the efficiency of monomer copolymerization in the polymerization system tends to decrease, which sometimes has a negative impact on the efficiency of industrial production; when the monomer concentration is above the upper limit, the vinyl chloride copolymer precursors are prone to agglomeration and adhesion.

[0167] In precipitation polymerization, the polymerization reaction can be carried out under dynamic or static conditions (i.e., without dynamic action), preferably under static conditions. Dynamic action can be applied by means of ultrasonic irradiation, stirring, or oscillation.

[0168] In the case of suspension polymerization, for example, suspension polymerization can be carried out by adding vinyl chloride, the monomer shown in formula (a') and optional other monomers to water containing a dispersant and polymerizing to obtain spherical or near-spherical copolymers.

[0169] In suspension polymerization, all monomers can be added at once, or various monomers can be added in batches.

[0170] In some specific embodiments, the total concentration of all monomers in the water containing the dispersant is preferably 15-70% by mass, more preferably 20-65% by mass, and even more preferably 25-60% by mass. When the total monomer concentration is below the lower limit, the efficiency of monomer copolymerization in the polymerization system tends to decrease, which sometimes has a negative impact on the efficiency of industrial production; when the monomer concentration is above the upper limit, the vinyl chloride copolymer precursors are prone to agglomeration and adhesion.

[0171] In suspension polymerization, polymerization reactions can occur under dynamic conditions. These dynamic conditions can be applied through methods such as ultrasonic irradiation, stirring, or oscillation.

[0172] <Step (2)>

[0173] In step (2), the vinyl chloride copolymer precursor is used as a macromolecular initiator to perform ring-opening polymerization of the lactone monomer shown in formula (b) to obtain a vinyl chloride polymeric plasticizer P1 comprising vinyl chloride-based units and units shown in formula (A1):

[0174] Where L1 is the group represented by the following formula (B1):

[0175]

[0176] In equations (A1), (B1), and (b), the details of R1, R2, Q, n, R3, p, and q are the same as those in equation (A). Furthermore, in equations (B1) and (b), R... 41 It is hydrogen.

[0177] In this invention, there are no particular restrictions on the amount of vinyl chloride copolymer precursor and lactone monomer fed, as long as the desired copolymer A1 can be obtained.

[0178] In some preferred embodiments, from the viewpoint of more easily obtaining the vinyl chloride-based polymeric plasticizer desired by the present invention, the feed ratio of the vinyl chloride copolymer precursor to the lactone monomer, calculated based on the molar ratio of hydroxyl groups in the vinyl chloride copolymer precursor to the lactone monomer, is preferably 1:10 to 1:120, more preferably 1:20 to 1:100, and even more preferably 1:30 to 1:80.

[0179] Furthermore, ring-opening polymerization can be carried out in the presence of a catalyst. Examples of catalysts include, but are not limited to, metal-based catalysts, such as sodium methoxide, sodium ethoxide, methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, calcium chloride, aluminum chloride, ferric chloride, stannous octoate, etc.; and non-metallic catalysts, such as 4-dimethylaminopyridine, sulfonic acid, phosphoric acid, imine diphosphonic acid, squaric acid, benzoic acid, guanidine, diphenyl phosphate, phosphazene, etc.

[0180] The amount of initiator can be 1 to 50% by mass relative to the total mass of all monomers, for example, 2 to 20% by mass.

[0181] In this invention, there are no particular limitations on the ring-opening polymerization conditions, which can be appropriately adjusted according to the polymerization method, monomer type, etc. In some specific embodiments, the polymerization temperature can be -10 to 150°C, more preferably 0 to 100°C, and even more preferably 10 to 60°C. In other specific embodiments, the polymerization time can be 1 to 24 hours, more preferably 1.5 to 12 hours, and even more preferably 2 to 6 hours.

[0182] In this invention, there are no particular limitations on the polymerization method for ring-opening polymerization, such as emulsion polymerization, suspension polymerization, solution polymerization, etc. Each polymerization method can be implemented using means known in the art. In some preferred embodiments, from the viewpoint of more easily obtaining the desired vinyl chloride-based polymeric plasticizer, ring-opening polymerization is preferably carried out using solution polymerization.

[0183] For example, solution polymerization can be carried out by dissolving a vinyl chloride copolymer precursor in a suitable solvent, then adding a lactone monomer to initiate ring-opening polymerization.

[0184] Examples of solvents include, but are not limited to: ether solvents such as dioxane and tetrahydrofuran; ketone solvents such as acetone, butanone, and cyclohexanone; haloalkane solvents such as dichloromethane and chloroform; etc. These solvents can be used alone or in combination of two or more.

[0185] In some specific embodiments, the total concentration of the vinyl chloride copolymer precursor in the solvent is preferably 1-50% by mass, more preferably 2-30% by mass, and even more preferably 5-26% by mass. When the concentration of the vinyl chloride copolymer precursor is below the lower limit, the efficiency of the ring-opening polymerization of the lactone monomer in the polymerization system tends to decrease, which is not conducive to the efficiency of industrial production; when the concentration of the vinyl chloride copolymer precursor is above the upper limit, the solubility of the vinyl chloride copolymer precursor tends to deteriorate, which is not conducive to the polymerization reaction.

[0186] In addition, polymerization reactions can be carried out under dynamic or static conditions.

[0187] <Step (3)>

[0188] In step (3), optionally, the vinyl chloride-based polymeric plasticizer P1 is reacted with an anhydride represented by formula (c) to obtain a vinyl chloride-based polymeric plasticizer P2 comprising vinyl chloride-based units and units represented by formula (A2).

[0189] R5(O=)COC(=O)R5 (c) Wherein, L2 is the group represented by the following formula (B2).

[0190] In formula (c), R5 is each independently a C1 to C12 alkyl group.

[0191] In equation (A2), the definitions of R1, R2, Q, and n are the same as those in equation (A').

[0192]

[0193] In equations (A2), (B2), and (c), the details of R1, R2, Q, n, R3, R5, p, and q are the same as those in equation (A). Furthermore, in equations (B2) and (c), R... 42 It is hydrogen or -OC (=O)R5, but all R in the vinyl chloride-based polymeric plasticizer P2 42 Not all of them are hydrogen.

[0194] In this invention, there are no particular restrictions on the amount of vinyl chloride-based polymeric plasticizer P1 and acid anhydride added, as long as the desired copolymer A2 can be obtained.

[0195] In some preferred embodiments, from the viewpoint of more easily obtaining the vinyl chloride-based polymeric plasticizer desired by the present invention, the feed ratio of vinyl chloride-based polymeric plasticizer P1 to acid anhydride is based on R in vinyl chloride-based polymeric plasticizer P1. 41 The molar ratio of the acid anhydride to the anhydride is preferably 2:1 to 1:3, more preferably 1:1 to 1:2, and even more preferably 1:1 to 1:1.5.

[0196] In addition, there are no particular restrictions on the reaction conditions between the vinyl chloride-based polymeric plasticizer P1 and the acid anhydride, and various conventional methods known in the art can be used.

[0197] <Other Steps>

[0198] The preparation method of the present invention may also include other steps as needed, such as separation, washing, drying of the products in each step, and steps of combining vinyl chloride copolymer A and / or vinyl chloride copolymer B with other plasticizers.

[0199] <<Venerine Chloride Resin Compositions>>

[0200] The vinyl chloride-based resin composition of the present invention includes a vinyl chloride-based resin and the plasticizer described above.

[0201] In this invention, relative to 100% of the total mass of the vinyl chloride-based resin, the content of the vinyl chloride-based polymeric plasticizer is preferably 5-60% by mass, more preferably 10-50% by mass, and even more preferably 15-50% by mass.

[0202] In addition to vinyl chloride-based resins and the specific vinyl chloride-based polymeric plasticizers described above, the vinyl chloride-based resin compositions of the present invention may optionally include other polymer components. Examples of other polymer components include other resins, such as other vinyl chloride-based resins, propylene-based resins, ethylene-based resins, polyester resins such as polyethylene terephthalate, styrene-based resins, fluoropolymers, silicone resins, polyamide-based resins, polyimide-based resins, etc.; rubbers, such as styrene-butadiene rubber, nitrile rubber, butyl rubber, chloroprene rubber, isoprene rubber, cis-butadiene rubber, ethylene propylene rubber, ethylene propylene diene rubber, silicone rubber; thermoplastic elastomers, such as 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, fluoropolymer-based thermoplastic elastomers, etc. They can be used alone or in combination of two or more.

[0203] Furthermore, the vinyl chloride-based resin compositions of the present invention may optionally include, in any amount, a variety of other additives commonly known in the art, such as fillers, pigments, plasticizers, ultraviolet absorbers, light stabilizers, matting agents, surfactants, leveling agents, surface conditioners, degassing agents, heat stabilizers, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, antibacterial agents, foaming agents, crosslinking agents, lubricants, etc. These may be used alone or in combination of two or more.

[0204] The vinyl chloride-based resin compositions of the present invention can be prepared by methods commonly known in the art. For example, all components constituting the vinyl chloride-based resin compositions of the present invention are mixed using standard mixing equipment such as a mixer, a Banbury or Brabender mixer, an extruder, a kneader, and a two-roll mill. There are no particular limitations on the method of preparation of the composition, and the above mixing can be carried out in a single-stage or multi-stage manner depending on the desired composition. There are also no particular limitations on the mixing temperature and mixing speed of the above mixing, and they can be appropriately selected according to the desired composition.

[0205] Examples of compositions of the present invention include, but are not limited to, solid blends and liquid mixtures (including solutions, emulsions and dispersions).

[0206] <<Molded Products Based on Vinyl Chloride Resins>>

[0207] The vinyl chloride-based resin molded articles of the present invention are made by using the above-described vinyl chloride-based resin composition of the present invention.

[0208] In this invention, examples of vinyl chloride resin molded articles include, but are not limited to, various vinyl chloride resin profiles (e.g., sheets or profiles), indwelling needles, tubing, films, etc.

[0209] Example

[0210] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0211] <<Evaluation Methods>>

[0212] The composition ratio of each structural unit of the copolymer used as a macromolecular initiator, the number-average molecular weight and molecular weight distribution (PDI) of the copolymer, the copolymer composition distribution, the composition ratio of each structural unit of the vinyl chloride lactone graft copolymer, the number-average molecular weight of the graft copolymer, and the mechanical properties, glass transition temperature and anti-migration properties of the blend after being used as a plasticizer for polyvinyl chloride.

[0213] <Copolymer Composition>

[0214] The composition of the vinyl chloride copolymer precursor was determined by a Bruker AV400 nuclear magnetic resonance spectrometer (THF-d8 as solvent).

[0215] The composition of vinyl chloride-based polymeric plasticizers is calculated by determining the grafting amount of lactone units based on the mass difference before and after the polymerization reaction. Furthermore, the q-value is calculated based on this grafting mass and the molecular weight of the lactone monomer used.

[0216] <Number-average molecular weight (Mn) and molecular weight distribution (PDI)>

[0217] The number-average molecular weight and molecular weight distribution of the copolymers were determined using a Waters-1515 gel permeation chromatography system with THF as the eluent and polystyrene as the standard.

[0218] Glass transition temperature (Tg)

[0219] The glass transition temperature was determined using a Mettler differential scanning calorimeter (DSC 3) at a heating rate of 10 °C / min and a heating range of -70 to 120 °C.

[0220] <Mechanical Properties>

[0221] Polyvinyl chloride resin, vinyl chloride-based polymer plasticizer, and heat stabilizer were put into an open mill for open milling and then hot-pressed with a hot press to prepare dumbbell-shaped specimens. The mechanical properties of the specimens were measured using a universal tensile testing machine at a working temperature of 25℃, a tensile rate of 50mm / min, and a gauge length of 50mm.

[0222] <Migration resistance>

[0223] The samples obtained in the <Mechanical Properties> section were placed in petroleum ether, deionized water, and ethanol, respectively, and placed at 25°C for 7 days. After drying in a vacuum oven, the mass before and after treatment was measured, and the amount of plasticizer migration was calculated by calculating the mass loss.

[0224] Transparency

[0225] The transmittance of the samples obtained in the <Mechanical Properties> section was tested after being placed at room temperature for 15 days. The transmittance was measured using a UV-Vis spectrophotometer, with a wavenumber range of 200–800 cm⁻¹. -1 , at 800cm -1 The transmittance at a given point characterizes its transparency; the higher the value, the better the transparency.

[0226] <<Example 1>>

[0227] Synthesis of Vinyl Chloride Copolymer Precursors

[0228] 250g of mixed solvent (methanol / dodecane = 1 / 5, mass ratio) was added to a 500mL reactor, along with 2.72g of hydroxyethyl acrylate (HEA), 62g of vinyl chloride (VCM), and 1.90g of initiator di(2-ethylhexyl) peroxide dicarbonate (EHP, added as a 65% toluene solution). The mixture was heated to 45℃ for precipitation polymerization. After 12 hours of polymerization, the vinyl chloride copolymer precursor FE1 was obtained.

[0229] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0230] 20g of dioxane and 2g of the copolymer precursor FE1 obtained above were added to a 50mL side-necked flask. 0.302g of diphenyl phosphate catalyst (the molar ratio of hydroxyl groups in the copolymer precursor to the catalyst was 1:1) and 6.20g of caprolactone monomer (the molar ratio of hydroxyl groups in the copolymer precursor to caprolactone was 1:45) were added. The reaction temperature was 45℃. After 8h of graft polymerization, vinyl chloride-based polymeric plasticizer PE1 was obtained.

[0231] <Preparation of Vinyl Chloride Resin Molded Articles>

[0232] 100 phr of PVC resin (S-70), 40 phr of the above-obtained vinyl chloride polymer plasticizer, and 4 phr of heat stabilizer (181) were stirred evenly at 70°C and placed in an oven at 60°C for 60 minutes to fully absorb the heat stabilizer. Then, the mixture was kneaded in a two-roll mill at 160°C for 5 minutes. After that, the mixture was pressed into sheets using a flat vulcanizing machine at 180°C for 4 minutes and then cold-pressed for 4 minutes. After standing at room temperature for 24 hours, the vinyl chloride resin sample E1 was obtained by cutting the sheet.

[0233] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0234] <<Example 2>>

[0235] Synthesis of Vinyl Chloride Copolymer Precursors

[0236] Except that the amounts of HEA and VCM were changed to 24.5g and 43.22g respectively, the vinyl chloride copolymer precursor FE2 was obtained in the same manner as in Example 1.

[0237] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0238] The vinyl chloride polymer plasticizer PE2 was obtained in the same manner as in Example 1, with the molar ratio of hydroxyl groups to caprolactone in the copolymer precursor being 1:45, replacing all other components of the vinyl chloride copolymer precursor FE1 with vinyl chloride copolymer precursor FE2.

[0239] <Preparation of Vinyl Chloride Resin Molded Articles>

[0240] Except that vinyl chloride-based polymeric plasticizer PE2 was used instead of vinyl chloride-based polymeric plasticizer PE1, vinyl chloride-based resin sample E2 was obtained in the same manner as in Example 1.

[0241] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0242] <<Example 3>>

[0243] Synthesis of Vinyl Chloride Copolymer Precursors

[0244] Except that the amounts of HEA and VCM were changed to 1.5g and 63.22g respectively, the vinyl chloride copolymer precursor FE3 was obtained in the same manner as in Example 1.

[0245] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0246] The vinyl chloride polymer plasticizer PE3 was obtained in the same manner as in Example 1, with the molar ratio of hydroxyl groups to caprolactone in the copolymer precursor being 1:45, replacing all other components of the vinyl chloride copolymer precursor FE1 with vinyl chloride copolymer precursor FE3.

[0247] It should be noted that, compared to Example 1, the precursor contains fewer HEA-based units, resulting in lower polymerization efficiency and conversion efficiency when initiating the polymerization of caprolactone, leading to increased costs and reduced production efficiency in the industry.

[0248] <Preparation of Vinyl Chloride Resin Molded Articles>

[0249] Except that the vinyl chloride polymeric plasticizer PE3 was used instead of the vinyl chloride polymeric plasticizer PE1, the vinyl chloride resin sample E3 was obtained in the same manner as in Example 1.

[0250] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0251] <<Example 4>>

[0252] Synthesis of Vinyl Chloride Copolymer Precursors

[0253] Except that the mixed solvent was changed to 250g of n-hexane, the vinyl chloride copolymer precursor FE4 was obtained in the same manner as in Example 1.

[0254] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0255] The vinyl chloride polymer plasticizer PE4 was obtained in the same manner as in Example 1, with the hydroxyl group to caprolactone molar ratio in the copolymer precursor being 1:45, replacing all other components of the vinyl chloride copolymer precursor FE1 with the vinyl chloride copolymer precursor FE4.

[0256] <Preparation of Vinyl Chloride Resin Molded Articles>

[0257] Except that the vinyl chloride polymeric plasticizer PE4 was used instead of the vinyl chloride polymeric plasticizer PE1, the vinyl chloride resin sample E4 was obtained in the same manner as in Example 1.

[0258] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0259] <<Example 5>>

[0260] Synthesis of Vinyl Chloride Copolymer Precursors

[0261] Except that the amounts of HEA and VCM were changed to 7.5g and 57.22g respectively, the vinyl chloride copolymer precursor FE5 was obtained in the same manner as in Example 1.

[0262] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0263] The vinyl chloride polymer plasticizer PE5 was obtained in the same manner as in Example 1, with the molar ratio of hydroxyl groups to caprolactone in the copolymer precursor being 1:45, replacing all other components of the vinyl chloride copolymer precursor FE1 with vinyl chloride copolymer precursor FE5.

[0264] <Preparation of Vinyl Chloride Resin Molded Articles>

[0265] Except that the vinyl chloride polymeric plasticizer PE5 was used instead of the vinyl chloride polymeric plasticizer PE1, the vinyl chloride resin sample E5 was obtained in the same manner as in Example 1.

[0266] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0267] <<Example 6>>

[0268] Synthesis of Vinyl Chloride Copolymer Precursors

[0269] Except that the amounts of HEA and VCM were changed to 15.5g and 49.22g respectively, the vinyl chloride copolymer precursor FE6 was obtained in the same manner as in Example 1.

[0270] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0271] The vinyl chloride polymer plasticizer PE6 was obtained in the same manner as in Example 1, with the hydroxyl group to caprolactone molar ratio in the copolymer precursor being 1:45, replacing all other components of the vinyl chloride copolymer precursor FE1 with the vinyl chloride copolymer precursor FE6.

[0272] <Preparation of Vinyl Chloride Resin Molded Articles>

[0273] Except that the vinyl chloride polymeric plasticizer PE6 was used instead of the vinyl chloride polymeric plasticizer PE1, the vinyl chloride resin sample E6 was obtained in the same manner as in Example 1.

[0274] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0275] <<Example 7>>

[0276] Synthesis of Vinyl Chloride Copolymer Precursors

[0277] Except that HEA, methyl methacrylate (MMA), and VCM were used as monomers and the feed amounts of HEA, MMA, and VCM were set to 3.8 g, 21.9 g, and 39.1 g, respectively, the vinyl chloride copolymer precursor FE7 was obtained in the same manner as in Example 1.

[0278] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0279] The vinyl chloride polymer plasticizer PE7 was obtained in the same manner as in Example 1, with the vinyl chloride copolymer precursor FE7 replacing all the vinyl chloride copolymer precursors except FE1, according to the molar ratio of hydroxyl groups to caprolactone in the copolymer precursor at 1:115.

[0280] <Preparation of Vinyl Chloride Resin Molded Articles>

[0281] Except that the vinyl chloride polymeric plasticizer PE7 was used instead of the vinyl chloride polymeric plasticizer PE1, the vinyl chloride resin sample E7 was obtained in the same manner as in Example 1.

[0282] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0283] <<Example 8>>

[0284] Synthesis of Vinyl Chloride Copolymer Precursors

[0285] Except that the mixed solvent was changed to 250g of methanol, the vinyl chloride copolymer precursor FE8 was obtained in the same manner as in Example 1.

[0286] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0287] The vinyl chloride polymer plasticizer PE8 was obtained in the same manner as in Example 1, with the hydroxyl group to caprolactone molar ratio in the copolymer precursor being 1:45, replacing all other components of the vinyl chloride copolymer precursor FE1 with the vinyl chloride copolymer precursor FE8.

[0288] <Preparation of Vinyl Chloride Resin Molded Articles>

[0289] Except that vinyl chloride-based polymeric plasticizer PE8 was used instead of vinyl chloride-based polymeric plasticizer PE1, vinyl chloride-based resin sample E8 was obtained in the same manner as in Example 1.

[0290] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0291] <<Example 9>>

[0292] Synthesis of Vinyl Chloride Copolymer Precursors

[0293] 250g of mixed solvent (methanol / dodecane = 1 / 5, mass ratio) was added to a 500mL reactor, along with 2.72g of propyl 2,3-dihydroxyacrylate (DDPA), 62g of vinyl chloride, and 1.90g of initiator di(2-ethylhexyl) peroxide dicarbonate (EHP, added as a 65% toluene solution). The mixture was heated to 45℃ for precipitation polymerization. After 12 hours of polymerization, the vinyl chloride copolymer precursor FE9 was obtained.

[0294] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0295] The vinyl chloride polymer plasticizer PE9 was obtained in the same manner as in Example 1, with the molar ratio of hydroxyl groups to caprolactone in the copolymer precursor being 1:50, replacing all other components of the vinyl chloride copolymer precursor FE1 with vinyl chloride copolymer precursor FE9.

[0296] <Preparation of Vinyl Chloride Resin Molded Articles>

[0297] Except that vinyl chloride-based polymeric plasticizer PE9 was used instead of vinyl chloride-based polymeric plasticizer PE1, vinyl chloride-based resin sample E9 was obtained in the same manner as in Example 1.

[0298] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0299] <<Example 10>>

[0300] Synthesis of Vinyl Chloride Copolymer Precursors

[0301] The vinyl chloride copolymer precursor FE1 was obtained in the same manner as in Example 1.

[0302] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0303] 20g of dioxane and 2g of the copolymer precursor FE1 obtained above were added to a 50mL side-mounted flask. 0.302g of diphenyl phosphate catalyst (molar ratio of hydroxyl to catalyst was 1:1) and 6.20g of caprolactone monomer (molar ratio of hydroxyl to caprolactone was 1:45) were added. The reaction temperature was 45℃, and after 8h of graft polymerization, a vinyl chloride-based polymeric plasticizer was obtained. Then, acetic anhydride was added to the polymerization system (the amount of acetic anhydride added was based on a molar ratio of acetic anhydride to hydroxyl in the copolymer precursor = 1.2:1), and the reaction was continued at the same temperature for 2h to obtain ester-terminated vinyl chloride-based polymeric plasticizer PE10.

[0304] <Preparation of Vinyl Chloride Resin Molded Articles>

[0305] Except that the vinyl chloride polymeric plasticizer PE10 was used instead of the vinyl chloride polymeric plasticizer PE1, the vinyl chloride resin sample E10 was obtained in the same manner as in Example 1.

[0306] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 1.

[0307] <<Comparative Example 1>>

[0308] Synthesis of Vinyl Chloride Copolymer Precursors

[0309] The vinyl chloride copolymer precursor FE1 was obtained in the same manner as in Example 1.

[0310] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0311] Except for adjusting the molar ratio of hydroxyl groups to caprolactone in copolymer precursor FE1 to 1:135, vinyl chloride-based polymeric plasticizer PC1 was obtained in the same manner as in Example 1.

[0312] <Preparation of Vinyl Chloride Resin Molded Articles>

[0313] Except that the vinyl chloride polymer plasticizer PE7 was used instead of the vinyl chloride polymer plasticizer PE1, the vinyl chloride resin sample C1 was obtained in the same manner as in Example 1.

[0314] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 2.

[0315] <<Comparative Example 2>>

[0316] Synthesis of Vinyl Chloride Copolymer Precursors

[0317] The vinyl chloride copolymer precursor FE1 was obtained in the same manner as in Example 1.

[0318] Synthesis of Vinyl Chloride-Based Polymer Plasticizers

[0319] Except for adjusting the molar ratio of hydroxyl groups to caprolactone in copolymer precursor FE1 to 1:8, vinyl chloride-based polymeric plasticizer PC2 was obtained in the same manner as in Example 1.

[0320] <Preparation of Vinyl Chloride Resin Molded Articles>

[0321] Except that the vinyl chloride polymer plasticizer PE7 was used instead of the vinyl chloride polymer plasticizer PE1, the vinyl chloride resin sample C2 was obtained in the same manner as in Example 1.

[0322] The obtained copolymer precursor, vinyl chloride-based polymeric plasticizer, and vinyl chloride-based resin samples were tested and evaluated as described above. The results are shown in Table 2.

[0323]

[0324] Table 2

[0325]

[0326] It should be noted that in Tables 1 and 2, "A'" represents the unit represented by formula A' in this invention, "A" represents the unit represented by formula A in this invention, "VCM" represents the unit based on vinyl chloride, and "MMA" represents the unit based on methyl methacrylate.

[0327] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0328] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A plasticizer, characterized in that, Including vinyl chloride-based polymeric plasticizers, said vinyl chloride-based polymeric plasticizers comprising vinyl chloride-based units and units represented by the following formula (A): In formula (A), R1 is independently hydrogen, C1-20 alkyl or C6-20 aryl, R2 is hydrogen, C1-8 alkyl or C6-12 aryl, Q is an organic group with an n+1 valence, L is the group shown in formula (B) below, and n is an integer from 1 to 5. In formula (B), R3 is each independently hydrogen or a C1-12 alkyl group, R4 is each independently hydrogen or -C(=O)R5, where R5 is a C1-12 alkyl group, p is an integer from 1 to 20, and q is an integer from 10 to 120.

2. The plasticizer according to claim 1, characterized in that, In formula (A), R1 is independently hydrogen, C1-10 alkyl or C6-10 aryl, R2 is hydrogen, C1-5 alkyl or C6-10 aryl, and n is an integer from 1 to 3; In formula (B), R3 is hydrogen or a C1-10 alkyl group, R4 is hydrogen or -C(=O)R5, where R5 is a C1-10 alkyl group, p is an integer from 3 to 15, and q is an integer from 15 to 120.

3. The plasticizer according to claim 1 or 2, characterized in that, Q is a group represented by formula (C) or formula (D): In formulas (C) and (D), * represents the connection with -OL, and R6 and R7 are each independently an n+1 valence group obtained by removing n+1 hydrogen atoms from an alkane, an n+1 valence group having an ether oxygen atom at the end of the aforementioned n+1 valence group and / or between carbon-carbon bonds, or an n+1 valence group obtained by removing n+1 hydrogen atoms from an aromatic hydrocarbon. The definition of n is the same as the definition of n in formula (A).

4. The plasticizer according to any one of claims 1 to 3, characterized in that, Relative to 100% of the total mass of the vinyl chloride-based polymer plasticizer, the content of the vinyl chloride-based unit is 2-60% by mass, and the content of the unit represented by formula (A) is 35-95% by mass.

5. The plasticizer according to any one of claims 1 to 4, characterized in that, The glass transition temperature of the vinyl chloride-based polymeric plasticizer is below 25°C; and / or The number average molecular weight (Mn) of the vinyl chloride-based polymeric plasticizer is 10,000 to 50,000; and / or The molecular weight distribution of the vinyl chloride-based polymeric plasticizer is 1.2 to 3.

5.

6. The plasticizer according to any one of claims 1 to 5, characterized in that, The vinyl chloride-based polymeric plasticizer is obtained based on a vinyl chloride-based copolymer precursor, which comprises vinyl chloride-based units and units represented by the following formula (A'): The definitions of R1, R2, Q, and n in equation (A') are the same as those in equation (A).

7. A method for preparing a plasticizer, characterized in that, include: (1) Copolymerize vinyl chloride with the monomer shown in formula (a') to obtain a vinyl chloride copolymer precursor comprising vinyl chloride-based units and units shown in formula (A'): In formulas (a') and (A'), R1 is independently hydrogen, a C1-20 alkyl group or a C6-20 aryl group, R2 is hydrogen, a C1-8 alkyl group or a C6-12 aryl group, Q is an organic group with an n+1 valence, and n is an integer from 1 to 5; (2) Using the vinyl chloride copolymer precursor as a macromolecular initiator, the lactone monomer shown in formula (b) is subjected to ring-opening polymerization to obtain a vinyl chloride polymeric plasticizer P1 comprising vinyl chloride-based units and units shown in formula (A1): In formula (b), R3 is each independently hydrogen or a C1-12 alkyl group, and p is an integer from 1 to 20. In formula (A1), the definitions of R1, R2, Q, and n are the same as those in formula (A'), and L1 is the group shown in formula (B1). In equation (B1), the definitions of R3 and p are the same as those in equation (b). 41 For hydrogen, q is an integer from 10 to 120; (3) Optionally, the vinyl chloride-based polymeric plasticizer P1 is reacted with an anhydride represented by formula (c) to obtain a vinyl chloride-based polymeric plasticizer P2 comprising vinyl chloride-based units and units represented by formula (A2). R5(O=)COC(=O)R5 (c) In formula (c), each of R5 is an alkyl group from C1 to C12. In formula (A2), the definitions of R1, R2, Q, and n are the same as those in formula (A'), and L2 is the group shown in formula (B2). In equation (B2), the definitions of R3 and p are the same as those in equation (b). 42 Each is independently hydrogen or -C(=O)R5, but all R in the vinyl chloride-based polymeric plasticizer P2 42 Not all are hydrogen, and q is an integer from 10 to 120.

8. The preparation method according to claim 7, characterized in that, In step (1), the number-average molecular weight Mn of the vinyl chloride copolymer precursor is 5000–20000, and / or the molecular weight distribution of the vinyl chloride copolymer precursor is 1.2–3.5; and / or In step (1), the content of the vinyl chloride-based unit is 50-95% by mass relative to 100% by mass of the total mass of the vinyl chloride copolymer precursor, and the content of the unit represented by formula (A') is 5-40% by mass; and / or In step (1), the copolymerization temperature is 40–70°C, and the copolymerization time is 2–24 hours; and / or In step (1), the copolymerization is carried out by suspension polymerization or precipitation polymerization.

9. The preparation method according to claim 7 or 8, characterized in that, In step (2), the feed ratio of the vinyl chloride copolymer precursor to the lactone monomer is calculated to be 1:10 to 1:120 based on the molar ratio of the hydroxyl group in the vinyl chloride copolymer precursor to the lactone monomer; and / or In step (2), the polymerization temperature is -10 to 150°C, and the polymerization time is 1 to 24 hours; and / or In step (2), the polymerization is carried out by solution polymerization.

10. A vinyl chloride-based resin composition, characterized in that: include: Vinyl chloride resins, and The plasticizer according to any one of claims 1 to 6, or the plasticizer obtained by the preparation method according to any one of claims 7 to 9.

11. A vinyl chloride-based resin molded article, characterized in that, The molded article is made by using the vinyl chloride-based resin composition according to claim 10.

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