CN112574349B - Rigid polyvinyl chloride-based copolymer, method for producing same, composition comprising same, and resin product made from composition - Google Patents

Abstract

The present invention relates to a rigid polyvinyl chloride-based copolymer, a method for preparing the same, a composition comprising the same, and a resin article made of the composition. The hard vinyl chloride copolymer comprises: the vinyl chloride-based structural unit (a), the structural unit (b) based on the monomer represented by the following formula (1), and optionally the structural unit (c) based on the monomer represented by the following formula (2) are contained in an amount of 2 to 20% by mass in total relative to the total mass of the vinyl chloride-based copolymer. CH (CH) ₂ ＝CR ₁ COO(R ₂ O) _x R ₃ (1)CH ₂ ＝CR ₄ COOR ₅ (2)。

Description

Rigid polyvinyl chloride copolymer, its preparation method, its composition and its Resin products made from compositions

technical field

The invention relates to the field of vinyl chloride resin synthesis, in particular to a rigid vinyl chloride copolymer, a preparation method thereof, a composition comprising the same and a resin product made from the composition.

Background technique

Polyvinyl chloride (PVC) resin is formed by free radical polymerization of vinyl chloride monomer (VC). It is one of the five general-purpose resins in synthetic materials. Its output is second only to polyethylene and polypropylene, ranking third in the world for general-purpose plastics. . Due to its excellent chemical resistance, chemical stability, thermoplasticity and low manufacturing cost, PVC resin is widely used in construction, water supply, daily use and biomedical fields.

Due to the relatively large polarity of the PVC molecular chain, the movement of the molecular chain is restricted, which increases the processing difficulty of PVC resin. Therefore, plasticizers should be added during the processing of polyvinyl chloride to reduce the melt viscosity and improve the flexibility of PVC. At present, phthalate esters (PAEs) plasticizers represented by dioctyl phthalate (DEHP) are mainly used (about 70%) in the processing of PVC resin. However, PAEs are toxic small-molecule plasticizers. During the use of PVC resin products, the plasticizer molecules are easy to migrate to the surface of the product, resulting in a decrease in product performance. Especially in the field of medical products, small molecule PAEs plasticizers will gradually migrate out of PVC resin products during use, enter blood or body fluids, or enter the human body through other contact routes, causing physiological hazards. At present, one of the research hotspots is to develop environmentally friendly non-toxic/low-toxic plasticizers. For this, despite the rapid development, it is still difficult to solve the problem of emigration of plasticizers.

Aiming at the migration problem of small molecule plasticizers, it is considered that an effective way is to prepare vinyl chloride copolymers by copolymerizing vinyl chloride and monomers with plasticizing function, so as to endow polyvinyl chloride resin with self-plasticizing properties. However, due to the characteristics of vinyl chloride monomer itself, such as low monomer activity, large monomer chain transfer constant, high free radical activity, and large difference in reactivity ratio with other conventional monomers, it is difficult for vinyl chloride to pass through with other monomers. Copolymerization is carried out by means of common free radical polymerization. Therefore, at present, the modified polyvinyl chloride resin is mainly prepared by PVC post-graft modification and living polymerization technology. Usually, for the evaluation of the migration resistance of the modified polyvinyl chloride resin, the consideration is whether there are components that are easy to migrate out due to the introduction of plasticizing components in the molecular chain, such as shorter molecules. chains or molecular chains with too high a content of plasticizing components, etc.

For example, in Non-Patent Document 1, the ring-opening reaction of caprolactone and propargyl alcohol is utilized to first synthesize alkynyl-terminated polycaprolactone (PCL-Alkyne), and then process it with azide-treated PVC resin ( PVC-N3) undergoes a click reaction under the irradiation of ultraviolet light, and successfully covalently grafts PCL-Alkyne onto the PVC side chain. DSC tests show that the introduction of PCL significantly reduces the glass transition temperature of PVC resin, and obtains Good self-plasticizing effect. However, the price of raw materials used in Non-Patent Document 1 is relatively high, and the production method is relatively complicated. Therefore, the main significance of this technology lies in scientific research, and it has no value for industrial application. Furthermore, the azide-treated PVC actually sacrifices the chlorine atoms in PVC that contribute greatly to the performance, which is unfavorable for practical use.

For example, in Non-Patent Document 2, a PVC-g-HPG graft copolymer with self-plasticizing properties was synthesized by a click reaction using azide-treated PVC and alkyne-containing hyperbranched polyglycidyl ether. Due to the covalent bonding of HPG-C6 to PVC, the amorphous, dendritic structure, and multiple polyether segments of HPG-C6, the PVC-g-HPG graft copolymer exhibited excellent flexibility and mechanical properties. When the grafting amount of HPG-C6 is 9%, the elongation at break is as high as 900%, and the migration rate of plasticizing components is almost zero, realizing a PVC resin with self-plasticizing effect. However, similar to the situation in Non-Patent Document 1, this technology also has practical problems such as complicated process, high cost, and unsuitable for large-scale preparation.

For example, non-patent literature 3 has reported that polyvinyl chloride is modified by living polymerization technology, using unstable chlorine on the PVC molecular chain as the reaction site, and using butyl acrylate and 2-ethylhexyl acrylate to modify polyvinyl chloride by ATRP method. The PVC resin was modified by graft polymerization, and PVC-BA and PVC-EHA graft polymers were synthesized. However, Non-Patent Document 3 does not pay attention to self-plasticizing properties. In addition, transition metal compounds often remain in the resin obtained by this technology, resulting in poor durability of the resin in actual use.

For example, in Non-Patent Document 4, the polyvinyl chloride resin is modified by reactive blending, and the PVC suspension material adsorbed with monomers, initiators, and crosslinking agents is obtained in-situ polymerization in a twin-screw extruder. Melt state blends such as PVC/PMMA, PVC/PVAc, PVC/PBA, PVC/PEHA. Since the reaction temperature in the extruder is 180°C, the obtained products are mostly low-molecular-weight polymers, which play the role of plasticizing PVC. However, PVC is prone to thermal decomposition under this process route, and the requirements for equipment are relatively high. High, difficult to industrial production.

For example, in Non-Patent Document 5, a butyl acrylate-vinyl chloride copolymer was 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 is likely to cause blocking. In addition, self-plasticizing properties are limited due to the low content of butyl acrylate-based structural units that can be incorporated into the resulting resin.

For example, non-patent literature 6 records that the suspension copolymerization of VC and BA has been studied by the method of single electron transfer-degenerate chain transfer living radical polymerization (SET-DTLRP), and polyvinyl chloride- Polybutylacrylate random copolymer (PVC-PBA), DMTA result shows, in this polyvinyl chloride-polybutylacrylate random copolymer, along with PBA content increases to 40% from 10% gradually, PVC-PBA chlorine The Tg of the ethylene copolymer resin also decreased from 70°C to 25°C. Although the living polymerization method is suitable for adjusting the structure of the obtained copolymer resin, this technology has high requirements on the production process and high cost. In addition, there are residual metal ions in the product, and there are shortcomings such as complicated post-treatment, and it has no industrial application value.

As mentioned above, most of the currently disclosed technologies are only at the stage of scientific research, and have low industrial practical value; while technologies suitable for industrial production are often difficult to achieve excellent self-plasticity and have poor control over product structure.

prior art literature

non-patent literature

Non-Patent Document 1: Eur.Polym.J., 2015, 66, 282–289.

Non-Patent Document 2: Macromol. Rapid Commun., 2016, 37, 2045-2051.

Non-Patent Document 3: J.Polym.Sci.: Part A: Polym.Chem., 2003, 41, 457–3462

Non-Patent Document 4: Polym. Adv. Technol. 2005, 16, 495–504.

Non-Patent Document 5: China Chlor-Alkali, 2013, 2, 17-22.

Non-Patent Document 6: Eur.Polym.J., 2015, 73, 202–211.

Contents of the invention

The problem to be solved by the invention

In view of the above-mentioned problems in the prior art, the object of the present invention is to provide a rigid vinyl chloride copolymer with excellent self-plasticization, processability and mechanical properties. On this basis, the products made of it also have excellent biological.

The object of the present invention is also to provide a preparation method of the above-mentioned vinyl chloride copolymer, a resin composition comprising the above-mentioned vinyl chloride copolymer, and an article made of the resin composition.

solutions to problems

In order to achieve the purpose of the above invention, the present invention provides a rigid vinyl chloride copolymer, a method for preparing a rigid vinyl chloride copolymer, and a product comprising the above-mentioned vinyl chloride copolymer, which have the following characteristics [1] to [10]. Resin composition and articles made from the resin composition.

[1] A rigid vinyl chloride copolymer, characterized in that it comprises: a structural unit (a) based on vinyl chloride, a structural unit (b) based on a monomer represented by the following formula (1), and optionally The structural unit (c) based on the monomer represented by the following formula (2),

CH ₂ =CR ₁ COO(R ₂ O) _x R ₃ (1)

In the formula (1), R ₁ is selected from hydrogen and straight-chain or branched-chain alkyl groups with 1 to 6 carbons; the number of repeating units x is an integer selected from 2 to 20, and each R ₂ is selected from The straight-chain or branched-chain alkylene groups with a carbon number of 2 to 10 may be the same or different; _R3 is selected from hydrogen and a straight-chain or branched-chain alkyl group with a carbon number of 1 to 4,

CH ₂ =CR ₄ COOR ₅ (2)

In the formula (2), _R4 is selected from hydrogen and methyl, and _R5 is selected from linear or branched alkyl groups with 1 to 18 carbons, linear or branched alkyls with 1 to 18 carbons. Branched hydroxyalkyl, straight or branched alkoxyalkyl with 1 to 18 carbons, straight or branched aminoalkyl with 1 to 18 carbons, Or a cycloalkyl group having 3 to 18 atoms without heteroatoms;

The total content of the structural unit (b) and the structural unit (c) is 2 to 20% by mass relative to the total mass of the rigid vinyl chloride copolymer.

[2] The rigid vinyl chloride copolymer according to [1], wherein the content of the structural unit (b) is 2 to 15% by mass based on the total mass of the rigid vinyl chloride copolymer.

[3] The rigid vinyl chloride copolymer according to [1] or [2], wherein the content of the structural unit (c) is 1 to 18% by mass based on the total mass of the rigid vinyl chloride copolymer.

[4] The rigid vinyl chloride copolymer according to any one of [1] to [3], wherein in the formula (1), R ₁ is selected from hydrogen and linear or branched chains having 1 to 4 carbons. Like alkyl group; the number of repeating units x is an integer selected from 2 to 15, and each R ₂ is selected from linear or branched alkylene groups with carbon numbers of 2 to 6, which may be the same or different.

[5] The rigid vinyl chloride-based copolymer according to any one of [1] to [4], which has a tensile elongation at break of 140% or less.

[6] The rigid vinyl chloride-based copolymer according to any one of [1] to [5], which has only one glass transition temperature.

[7] The rigid vinyl chloride copolymer according to any one of [1] to [6], which has a number average molecular weight of 40,000 to 250,000.

[8] A method for preparing the rigid vinyl chloride copolymer according to any one of [1] to [7], comprising: vinyl chloride, the monomer represented by the formula (1) and optionally The raw material of the monomer represented by the said formula (2) carries out copolymerization reaction.

[9] A vinyl chloride-based resin composition comprising the rigid 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].

The effect of the invention

The present invention provides a rigid vinyl chloride copolymer having excellent self-plasticizing properties, processability and mechanical properties. By copolymerizing vinyl chloride and the monomer represented by the above formula (1) at a specific ratio to introduce plasticizing segments into the molecular chain of polyvinyl chloride, the obtained vinyl chloride copolymer not only has The excellent mechanical properties of the resin can also be plasticized and shaped well even without adding a plasticizer during processing, thereby avoiding the degradation of the performance of the resin product and the environment caused by the migration of the plasticizer. pollute. In addition, the monomer represented by the above formula (1) also provides biocompatibility. Therefore, the goods made of the vinyl chloride copolymer of the present invention not only can not contain plasticizer, but also have good biological properties (such as no cytotoxicity, good biocompatibility, no blood coagulation, etc.), so that the present invention Products made of the inventive vinyl chloride copolymer have good biological properties and can be used for medical purposes.

Further, by further copolymerizing vinyl chloride and the monomer represented by the above formula (1) with the monomer represented by the above formula (2) that can be used as an auxiliary plasticizing monomer, the plasticizer in the vinyl chloride copolymer can be adjusted as required. The composition of the plastic segment, thereby further improving the self-plasticization, processability and mechanical properties (such as improved toughness) of the vinyl chloride copolymer and providing excellent water resistance and lower cost.

The present invention also provides a method for producing the above-mentioned vinyl chloride copolymer, which realizes the copolymerization of vinyl chloride and comonomers through a convenient method that is beneficial to industrial production.

The present invention further provides a vinyl chloride-based resin composition comprising the above-mentioned vinyl chloride-based copolymer and a resin article made from the resin composition.

Detailed ways

Hereinafter, the content of the present invention will be described in detail. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted:

In the present specification, the numerical range represented by "numerical value A to numerical value B" refers to a range including numerical values A and B at the endpoints.

In this specification, the term "(meth)acrylate" is a concept covering both methacrylate and acrylate.

In this specification, the repeating unit formed directly by the polymerization of the monomer and the unit formed by chemically converting a part or all of the substituents of the repeating unit formed by the polymerization of the monomer into other substituents are collectively referred to as "structural unit". .

In this specification, unless otherwise specified, "%" means mass percentage.

In this specification, the meaning expressed by "may" includes the meaning of performing certain processing and not performing certain processing.

In this specification, "optional" or "optionally" means that the next described event or situation may or may not occur, and that the description includes situations where the event occurs and situations where the event does not occur.

In this specification, references to "some specific/preferred embodiments", "other specific/preferred embodiments", "embodiments" and the like refer to specific elements described in relation to the embodiments (for example, A feature, structure, property and/or characteristic) is included in at least one embodiment described herein and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

<Vinyl chloride copolymer>

The rigid 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 optionally a structural unit based on the following formula (2 ) is a structural unit (c) of a monomer represented by ).

CH ₂ =CR ₁ COO(R ₂ O) _x R ₃ (1)

In the formula (1), R ₁ is selected from hydrogen and straight-chain or branched-chain alkyl groups with 1 to 6 carbons; the number of repeating units x is an integer selected from 2 to 20, and each R ₂ is selected from The linear or branched alkylene groups with 2 to 10 carbons may be the same or different; _R3 is selected from hydrogen and linear or branched alkyls with 1 to 4 carbons.

CH ₂ =CR ₄ COOR ₅ (2)

In the formula (2), _R4 is selected from hydrogen and methyl, and _R5 is selected from linear or branched alkyl groups with 1 to 18 carbons, linear or branched alkyls with 1 to 18 carbons. Branched hydroxyalkyl, straight or branched alkoxyalkyl with 1 to 18 carbons, straight or branched aminoalkyl with 1 to 18 carbons, Or a cycloalkyl group having 3 to 18 atoms that does not have a heteroatom.

The total content of the structural unit (b) and the structural unit (c) is 2 to 20% by mass relative to the total mass of the rigid vinyl chloride copolymer.

In some specific embodiments, the rigid vinyl chloride copolymer of the present invention includes structural units (a) based on vinyl chloride and structural units (b) based on monomers represented by formula (1), and do not include structural units based on formula (1) Structural unit (c) of the monomer represented by (2). In some preferred embodiments, the rigid vinyl chloride copolymer of the present invention includes structural units (a) based on vinyl chloride, structural units (b) based on monomers represented by formula (1) and structural units based on formula (2) The structural unit (c) of the monomer shown is three.

Each structural unit in the vinyl chloride copolymer of the present invention is described in detail below.

(structural unit (a))

The structural unit (a) is a vinyl chloride-based structural unit.

(structural unit (b))

The structural unit (b) is a structural unit derived from a monomer represented by the following formula (1).

CH ₂ =CR ₁ COO(R ₂ O) _x R ₃ (1)

In the vinyl chloride copolymer of the present invention, the structural unit (b) provides a plasticizing effect to reduce the polarity and rigidity of the polymer molecular chain and improve processability. The monomer represented by the above formula (1) has good copolymerizability with vinyl chloride, and can be copolymerized with vinyl chloride in a wide range of ratios even in a common radical polymerization system.

In formula (1), R ₁ is selected from hydrogen and a straight-chain or branched alkyl group with 1 to 6 carbons, preferably selected from hydrogen and a straight-chain or branched chain with 1 to 4 carbons. Alkyl is more preferably hydrogen or/and methyl.

In formula (1), the number of repeating units x is an integer selected from 2 to 20, and from the viewpoint of obtaining more excellent self-plasticization and further suppressing segment migration, the number of repeating units x is preferably an integer selected from 2 to 15 , more preferably an integer selected from 2-10. Each R ₂ is selected from linear or branched alkylene groups having 2 to 10 carbons, preferably from the viewpoint of obtaining more excellent self-plasticizing properties and further suppressing segment migration, preferably from 2 to 10 carbons. The linear or branched alkylene group of 6 is more preferably selected from linear or branched alkylene groups having 2 to 4 carbon atoms. Each R ₂ may be the same or different.

R ₃ is selected from hydrogen and linear or branched alkyl groups having 1 to 4 carbons.

When each R ₂ is the same, specific examples of monomers represented by the above formula (1) include but are not limited to polyethylene glycol methyl ether (meth)acrylate, polyethylene glycol ethyl ether (meth)acrylate, poly Polyethylene glycol propyl ether (meth)acrylate, polyethylene glycol butyl ether (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol methyl ether (meth)acrylate, polypropylene glycol Diethyl ether (meth)acrylate, polypropylene glycol propyl ether (meth)acrylate, polypropylene glycol butyl ether (meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol methyl ether (meth)acrylate Acrylates, Polybutylene Glycol Ether (Meth)acrylate, Polybutylene Glycol Propyl Ether (Meth)acrylate, Polybutylene Glycol Butyl Ether (Meth)acrylate, Polybutylene Glycol Mono(Meth)acrylate Acrylate. These monomers may be used alone or in combination of two or more.

When each R ₂ is different, the monomer shown in the above formula (1) can be represented by the structural formula shown in formula (1a):

CH ₂ =CR ₁ COO(R _2a O) _a (R _2b O) _b R ₃ (1a),

Preferably, in formula (1a), R ₁ and R ₃ are as defined above; R _2a is ethylene, R _2b is propylene, the number of repeating units a is selected from 1-3, and the number of repeating units b is selected from 1-12 .

(structural unit (c))

The structural unit (c) is a structural unit derived from a monomer represented by the following formula (2).

CH ₂ =CR ₄ COOR ₅ (2)

In the vinyl chloride-based copolymer of the present invention, the structural unit (c) provides an auxiliary plasticizing effect and further improves the mechanical properties and water resistance of the vinyl chloride-based copolymer.

In formula (2), R ₄ is selected from hydrogen and methyl, R ₅ is selected from linear or branched alkyl groups with 1 to 18 carbons, linear or branched alkyls with 1 to 18 carbons hydroxyalkyl, linear or branched alkoxyalkyl with 1 to 18 carbons, straight or branched aminoalkyl with 1 to 18 carbons, with or without A cycloalkyl group having 3 to 18 atoms having heteroatoms such as oxygen, nitrogen and sulfur.

It should be noted that "a straight-chain or branched alkoxyalkyl group with 1 to 18 carbons" means a straight or branched chain with a total carbon number of 1 to 18, and any The hydrogen atom is replaced by an alkyl group of an alkoxy group.

Specific examples of monomers 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, (meth) Tert-amyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate ester, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, undecyl (meth)acrylate ester, isoundecyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclooctyl (meth)acrylate, glycidyl (meth)acrylate , hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, (meth) Methoxypropyl acrylate, Ethoxypropyl (meth)acrylate, Dimethylaminomethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Dimethylaminopropyl (meth)acrylate . These monomers may be used alone or in combination of two or more.

From the standpoint of copolymerizability with other monomers and the self-plasticizing and mechanical properties of the resulting copolymer, (meth)acrylate monomers having a glass transition temperature of their homopolymers lower than 60° C. are preferred; wherein, More preferred are methyl acrylate, ethyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, (meth) At least one of isooctyl acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl acrylate, dimethylaminoethyl (meth)acrylate, and hexyl (meth)acrylate.

(Content of structural units (a), (b) and (c))

As long as the total content of structural unit (b) and structural unit (c) in the vinyl chloride copolymer of the present invention is 2 to 20% by mass, the structural unit (a), structural unit (b) and optional structural The content of each unit (c) is not particularly limited, and can be appropriately selected according to the use of the vinyl chloride-based copolymer. From the point of view of better improving the self-plasticization and mechanical properties of the vinyl chloride copolymer and better making the vinyl chloride copolymer of the present invention suitable for the application field of rigid PVC, the structural unit in the vinyl chloride copolymer The total content of (b) and the structural unit (c) is preferably 2 to 19% by mass, more preferably 3 to 18% by mass.

In the present invention, in some preferred embodiments, relative to the total mass of the vinyl chloride copolymer, the content of the structural unit (a) is preferably 80 to 98% by mass, more preferably 81 to 95% by mass, and even more preferably It is 84 to 92% by mass. When the content of the structural unit (a) is greater than the above preferred range, the resulting vinyl chloride-based copolymer tends to deteriorate in self-plasticity, processability and biological properties. When the content of the structural unit (a) is less than the above range, the mechanical properties of the resulting vinyl chloride copolymer tend not to meet the requirements for mechanical properties of rigid vinyl chloride resins.

In the present invention, in some preferred embodiments, relative to the total mass of the vinyl chloride copolymer, the content of the structural unit (b) is preferably 2 to 15% by mass, more preferably 2.5 to 12% by mass, and even more preferably 3% by mass. ~10% by mass. When the content of the structural unit (b) is greater than the above-mentioned preferred range, although the vinyl chloride copolymer has a significant plasticizing effect, the mechanical properties of the resulting vinyl chloride copolymer tend to decline, and even do not meet the requirements of rigid vinyl chloride copolymers. Requirements for certain application fields of resins; when the content of the structural unit (b) is less than the above range, the self-plasticizing, processability and biological properties of the obtained vinyl chloride copolymer tend to deteriorate.

In the preferred embodiment in which the rigid vinyl chloride copolymer of the present invention includes the structural unit (c), from the viewpoint of better self-plasticizing, mechanical properties, water resistance and cost reduction, relative to the vinyl chloride copolymer The total mass of the structural unit (c) is preferably 1-18% by mass, more preferably 2-17% by mass, still more preferably 4-16.5% by mass, still more preferably 5-16% by mass.

In some other preferred embodiments, relative to the total mass of the vinyl chloride-based copolymer, the respective contents of the structural unit (a), structural unit (b) and structural unit (c) simultaneously satisfy the above-mentioned ranges. For example, the structural unit (a) is preferably 80 to 98% by mass, the content of the structural unit (b) is preferably 2 to 15% by mass, and the content of the structural unit (c) is preferably 1 to 18% by mass.

(Structural units based on other monomers)

Within the scope of not impairing the technical effect of the present invention, in addition to the structural unit (a) based on vinyl chloride, the structural unit (b) based on the monomer shown in formula (1) and the optional monomer based on formula (2) In addition to the structural unit (c) of the monomer, the rigid vinyl chloride copolymer of the present invention may also include structural units based on other monomers.

There is no particular limitation on other monomers as long as they can be copolymerized with any one of vinyl chloride, monomers represented by formula (1), and optionally monomers represented by formula (2).

In the present invention, it is preferred that examples of structural units based on other monomers include, but not limited to, structural units based on vinyl ether monomers, structural units based on fluorine-containing (meth)acrylate monomers, structural units based on A structural unit based on a maleimide-based monomer, a structural unit based on an acrylonitrile-based monomer, and a structural unit based on a carboxyl group-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 required.

Structural units based on vinyl ether monomers

The structural unit derived from a vinyl ether monomer is a structural unit derived from a monomer represented by the following formula (3).

CH ₂ =CHOR ₆ (3)

In formula (3), R ₆ is selected from linear or branched alkyl groups with 1 to 10 carbons, linear or branched cycloalkyl groups with 3 to 10 carbons, and 1 to 10 carbons. 10 is a linear or branched hydroxyalkyl group, which may be substituted by halogen atoms such as chlorine, bromine, or fluorine. Preferably, R _is selected from linear or branched alkyl groups with 1 to 8 carbons, linear or branched cycloalkyl groups with 3 to 8 carbons, and straight or branched cycloalkyls with 1 to 8 carbons. Chain or branched hydroxyalkyl groups may be substituted by halogen atoms such as chlorine, bromine, or fluorine. In addition, the hydrogen atom in the formula (3) (meaning the hydrogen atom in "CH ₂ =CH-" in the formula (3)) may also be replaced by a halogen atom such as chlorine, bromine, fluorine or the like.

Examples of monomers 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 tert-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 rigid vinyl chloride-based copolymer of the present invention has a structural unit based on the monomer of the above formula (3), it can provide more excellent self-plasticity and also provide more excellent biocompatibility and lubricity.

Structural units based on fluorine-containing (meth)acrylate monomers

The structural unit derived from a fluorine-containing (meth)acrylate monomer is a structural unit derived from a monomer represented by the following formula (4).

CH ₂ =CR ₄ COOR ₇ (4)

In formula (4), R ₄ is as defined above, and R ₇ is selected from linear or branched fluoroalkyl groups with 1 to 18 carbons, fluorocycloalkyl groups with 3 to 18 carbons, and fluorine The substituted phenyl group is preferably selected from linear or branched fluoroalkyl groups having 1 to 12 carbon atoms, fluorocycloalkyl groups having 3 to 12 carbon atoms, and fluorophenyl groups. In addition, the hydrogen atom in the formula (4) (meaning the hydrogen atom in "CH ₂ =" in the formula (4)) may also be replaced by a halogen atom such as chlorine, bromine, fluorine or the like.

Examples of monomers represented by the above formula (4) include, but are not limited to, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, pentafluoropropyl (meth)acrylate, (meth) Pentafluorophenyl acrylate, hexafluorobutyl (meth)acrylate, heptafluorobutyl (meth)acrylate, octafluoropentyl (meth)acrylate, nonafluorohexyl (meth)acrylate, (meth) Dodecafluoroheptyl acrylate, tridecafluorooctyl (meth)acrylate. Among them, trifluoroethyl (meth)acrylate, pentafluorophenyl (meth)acrylate, and hexafluorobutyl (meth)acrylate are preferable. These monomers may be used alone or in combination of two or more.

When the rigid vinyl chloride copolymer of the present invention has a structural unit based on the monomer of the above formula (4), it can provide excellent processing lubricity (such as reducing adhesion to twin rolls or screws, reducing melt viscosity, etc.) and antimicrobial/fouling resistance of the product.

Structural units based on maleimide monomers

Examples of maleimide-based monomers forming maleimide-based monomer-based structural units 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 units based on acrylonitrile monomers

Examples of the acrylonitrile-based monomer forming the structural unit based on the acrylonitrile-based monomer include, without limitation, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. These monomers may be used alone or in combination of two or more.

Structural units based on carboxyl-containing monomers

Examples of carboxyl-containing monomers that form structural units based on carboxyl-containing monomers include, without limitation, acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypropyl (meth)acrylate, (meth) Carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These monomers may be used alone or in combination of two or more.

(glass transition temperature (Tg))

The glass transition temperature of the vinyl chloride copolymer of the present invention can reflect the structural characteristics of the copolymer, and can be used to express self-plasticizing properties.

From the viewpoint of obtaining more excellent self-plasticization and processability, the vinyl chloride-based copolymer of the present invention preferably has only one glass transition temperature. Further, generally, the glass transition temperature is not particularly limited. However, the glass transition temperature is preferably below 80°C, more preferably below 75°C. When the glass transition temperature is greater than or equal to the above upper limit, self-plasticization and processability of the vinyl chloride-based copolymer of the present invention tend to deteriorate. From the viewpoint of further securing the performance of the rigid vinyl chloride-based copolymer, the glass transition temperature is preferably 40°C or higher, more preferably 50°C or higher.

In the present invention, the glass transition temperature can be measured by a dynamic thermomechanical analyzer (DMTA).

(number average molecular weight)

The number average molecular weight of the vinyl chloride-based copolymer of the present invention is not particularly limited, and may be appropriately selected according to the application. From the viewpoint of simultaneously achieving better mechanical properties and lower cost, the number average molecular weight of the vinyl chloride copolymer of the present invention is preferably 40,000-250,000, more preferably 50,000-220,000, and still more preferably 50,000-200,000. When the number average molecular weight is smaller than the above range, the mechanical properties of the copolymer resin such as tensile strength and tensile elongation at break tend to decrease. When the number average molecular weight is larger than the above range, the required polymerization temperature tends to be too low, resulting in a low conversion rate and an increase in production cost.

In the present invention, the number average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

(physical properties)

According to the understanding of resin processability in this field, polyvinyl chloride usually needs to be processed under the situation of adding plasticizer, therefore, polyvinyl chloride resin is divided into rigid polyvinyl chloride ( For example, the content of plasticizer is less than 20%) and soft polyvinyl chloride (for example, the content of plasticizer is more than 20%), etc., and they are different in physical properties such as mechanical properties. However, since the vinyl chloride-based copolymer of the present invention can be processed excellently even without the addition of a plasticizer, whether the polyvinyl chloride-based copolymer is judged in the present invention is mainly based on the range of tensile elongation at break. Meet the requirements for rigid PVC in this field. Specifically, in the present invention, the tensile elongation at break of the vinyl chloride copolymer is preferably 140% or less according to the test method of GB/T 1040-2006, more preferably 10 to 140%, and even more preferably 11% ~138%, even more preferably 12-135%.

In the present invention, the tensile strength of the vinyl chloride copolymer is preferably above 30 MPa, more preferably above 35 MPa according to the test method of GB/T 1040-2006.

In the present invention, the hardness of the vinyl chloride copolymer is preferably greater than 70, more preferably greater than 75 according to the GB/T 2411-2008 test method (Shore D).

More preferably, the rigid vinyl chloride copolymer of the present invention simultaneously satisfies all the above-mentioned physical property parameters.

<Manufacturing method of rigid vinyl chloride copolymer>

The preparation method of the rigid vinyl chloride copolymer of the present invention is the preparation method of the above rigid vinyl chloride copolymer, which comprises: comprising vinyl chloride, monomers represented by the above formula (1) and optional above formula The raw materials of the monomers shown in (2) are copolymerized.

The details of vinyl chloride, the monomer represented by formula (1), the monomer represented by formula (2) and other monomers have been described above, and will not be repeated here.

Examples of copolymerization reactions of the present invention include, without limitation, block polymerization, random polymerization, graft polymerization, gradient polymerization. Among them, random polymerization is preferable from the viewpoint of expressing the technical effect of the present application more favorably, that is, the molecular chain of the rigid vinyl chloride-based copolymer of the present invention preferably has a random structure. More preferably, the rigid vinyl chloride copolymer of the present invention is a random copolymer.

As long as the rigid vinyl chloride copolymer of the present invention can be obtained, the mechanism of the preparation method is not particularly limited, and ordinary radical polymerization methods, living radical polymerization methods, etc. can be used. However, from the viewpoint of being advantageous for industrial production, the production method of the rigid vinyl chloride-based copolymer of the present invention is based on an ordinary radical polymerization mechanism.

As the polymerization method, any polymerization method that can be carried out based on a radical polymerization mechanism, such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, slurry polymerization, gas phase polymerization, interfacial polymerization, etc., can be used. From the viewpoint 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 method of the present invention is a well-known bulk polymerization method in the art. Specifically, the bulk polymerization method of the present invention is a polymerization method that does not include a dispersion medium in the polymerization system. Preferably, the bulk polymerization method is implemented by polymerizing each monomer used in the present invention in the presence of an initiator.

In the case of the bulk polymerization method, there is no limitation on the order and manner of adding the monomers, and the monomers may be added together or in batches in any combination.

Specific examples of initiators suitable for bulk polymerization include, but are not limited to: azo initiators such as azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanonitrile, etc.; organic peroxides Initiators such as tert-butyl peroxyneheptanoate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, peroxybis(hexadecyl)dicarbonate, tert-butyl peroxyneodecanoate Pentyl ester, tert-butyl peroxypivalate, bis-(4-tert-butylcyclohexyl peroxydicarbonate), dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, diisopropyl peroxydicarbonate Butyl ester, bis(2-ethylhexyl)peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, ditetradecyl peroxydicarbonate, tert-butyl peroxyacetate, new peroxide Cumyl decanoate, di-tert-butyl peroxide, cyclohexylsulfonyl peroxide, dibenzoyl peroxide, diisobutyryl peroxide, 1,1,3,3-tetradecanoic acid peroxide Methyl butyl, di-3-methoxybutyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, etc. These radical initiators may be used alone or in combination of two or more. In particular, radical initiators having a decomposition temperature of less than 80° C. are preferred.

The amount of the initiator used is preferably 0.001 to 4 mass%, more preferably 0.01 to 2 mass%, based on the total mass of the monomers.

Polymerization conditions can be appropriately selected according to the monomer composition, the decomposition temperature of the initiator, and the like. The polymerization temperature is preferably 0 to 100°C, more preferably 10 to 90°C, most preferably 30 to 80°C. The polymerization time is preferably 1 to 72 hours, more preferably 1 to 24 hours, most preferably 1 to 12 hours.

(suspension polymerization method)

The suspension polymerization method of the present invention is a well-known suspension polymerization method in the art. Preferably, the suspension polymerization method of the present invention is carried out with agitation applied to the polymerization system.

The dispersion medium in the suspension polymerization method may be water or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent may include without limitation: alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, etc.; Hexanone, etc.; Polyol 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; polyol 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, 2 -pyrrolidone, 1,3-dimethylimidazolidinone and ε-caprolactam; amides such as formamide, N-methylformamide, formamide and N,N-dimethylformamide; amines such as monoethanolamine, di Ethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane, and thiodiethanol; propylene carbonate and ethylene carbonate.

From the viewpoint of easy recovery, the dispersion medium is preferably water. Regarding water, various forms such as tap water, deionized water, and distilled water can be used.

The dispersant in the suspension polymerization method can be a well-known dispersant in the art, such as anionic dispersant, cationic dispersant, nonionic dispersant, polymer dispersant.

Specific examples of dispersants may include but are not limited to: water-soluble organic polymer substances, for example, partially hydrolyzed polyvinyl alcohol, polyacrylic acid or polymethacrylic acid salts, such as maleic anhydride/styrene copolymers and other synthetic high Molecules, such as methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose and other cellulose derivatives, such as gelatin, protein, starch, sodium alginate and other natural polymers; and water-insoluble inorganic powders, such as, Magnesium carbonate, calcium carbonate, barium sulfate, calcium sulfate, calcium phosphate, talc, kaolin; etc. These dispersants may be used alone or in combination of two or more. Considering the particle size and shape of the product, the transparency and film-forming properties of the resin, it is preferred to use a water-soluble organic polymer, more preferably a mixture of polyvinyl alcohol and cellulose derivatives. The usage-amount of a dispersing agent is preferably 0.01-5 mass % with respect to 100 mass parts of dispersion media, More preferably, it is 0.05-3 mass %.

The monomer concentration in the system is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, based on the total mass of the dispersion medium.

In the case of employing the suspension polymerization method, there are no restrictions on the order and manner of adding the monomers, and the monomers may be added together or in batches in any combination.

The types of initiators suitable for the suspension polymerization method, the amount of the initiator used, and the polymerization conditions (polymerization temperature and polymerization time, etc.) are the same as in the above-mentioned "(bulk polymerization method)", and will not be repeated here.

(emulsion polymerization method)

The emulsion polymerization method of the present invention is a well-known emulsion polymerization method in the art. Preferably, the emulsion polymerization method of the present invention is carried out in a state where stirring is applied to the polymerization system.

The type of the dispersion medium is the same as that in the above "(suspension polymerization method)", and will not be repeated here.

The monomer concentration in the system is preferably 5 to 60% by mass, more preferably 10 to 40% by mass relative to the total mass of the dispersion medium.

The emulsifier in the emulsion polymerization method may be a well-known emulsifier 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 polyethylene glycol ether, polyoxyalkylene sorbitan fatty acid ester, sorbitan fatty acid ester, etc.; anionic emulsifier, Such as fatty acid soaps, abietic acid soaps, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfate ester salts, alkyl sulfosuccinates, and sulfuric acid for nonionic emulsifiers with polyoxyalkylene chains Ester salts, phosphate ester salts, ether carboxylates, sulfosuccinates, etc.; cationic emulsifiers, such as stearyl trimethyl ammonium salt, cetyl trimethyl ammonium salt, lauryl trimethyl ammonium salt , dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkyldimethylhydroxyethylammonium salt, etc.

The usage-amount of an emulsifier is preferably 0.5-15 mass % with respect to 100 mass parts of dispersion media, More preferably, it is 1.0-10 mass %.

In addition, an emulsifier may not be used in the emulsion polymerization method of this invention, that is, the emulsion polymerization method of this invention may be based on a self-emulsion polymerization method.

In the case of employing the emulsion polymerization method, there are no restrictions on the order and manner of adding the monomers, and the monomers may be added together or in batches in any combination.

Specific examples of initiators suitable for emulsion polymerization include, but are not limited to: the initiators described above in "(bulk polymerization)"; redox initiators; persulfates such as ammonium persulfate, potassium persulfate, and the like. These initiators may be used alone or in combination.

The amount of the initiator used is preferably 0.001 to 4 mass%, more preferably 0.01 to 2 mass%, based on the total mass of the monomers.

Polymerization conditions can be appropriately selected according to the monomer composition, the decomposition temperature of the initiator, and the like. The polymerization temperature is preferably 10 to 90°C, most preferably 30 to 80°C. The polymerization time is preferably 1 to 72 hours, more preferably 1 to 24 hours, most preferably 1 to 12 hours.

<Vinyl chloride resin composition>

The vinyl chloride-based resin composition of the present invention includes the above-mentioned rigid vinyl chloride-based copolymer.

In addition to the rigid vinyl chloride-based copolymer of the present invention, the vinyl chloride-based resin composition of the present invention may optionally include other components, examples of which include other resins such as other vinyl chloride-based resins, propylene-based Resin, vinyl resin, polyester resin such as polyethylene terephthalate, styrene resin, fluororesin, silicone resin, polyamide resin, polyimide resin, etc.; rubber, such as butadiene Styrene rubber, nitrile rubber, butyl rubber, neoprene rubber, isoprene rubber, 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. These can be used alone, or in combination of two or more. The content of the above-mentioned other components is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 0 parts by mass relative to 100 parts by mass of the vinyl chloride resin composition.

The vinyl chloride resin composition of the present invention may also optionally contain various additives generally known in the art, such as fillers, pigments, plasticizers, ultraviolet absorbers, light stabilizers, matting agents, surface Activator, leveling agent, surface conditioner, degassing agent, heat stabilizer, antistatic agent, rust inhibitor, silane coupling agent, antifouling agent, antibacterial agent, foaming agent, crosslinking agent, lubricant, etc. . These can be used alone, or in combination of two or more. In some preferred embodiments, since the vinyl chloride-based copolymer of the present invention has excellent self-plasticizing properties, the vinyl chloride-based resin composition of the present invention does not contain a plasticizer.

The vinyl chloride-based resin composition of the present invention can be produced by methods 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 Banbury or Brabender mixers, extruders, kneaders, and two-roll mixers. There is no particular limitation on the preparation method of the composition, and the above-mentioned mixing may be performed in a single-stage or multi-stage manner according to the desired composition of the composition. The mixing temperature and mixing speed of the above-mentioned mixing are also not particularly limited, and may be appropriately selected according to the desired composition of the composition.

<Resin products>

The resin product of the present invention is a rigid PVC molded product made of the above-mentioned vinyl chloride-based resin composition. In some specific embodiments, the resin product of the present invention is preferably a melt-molded product, for example, obtained by extrusion molding, injection molding, blow molding, mold (pressurization) molding, calender molding, etc. Formed products.

The resin product of the present invention can be used in various applications known in the art, for example, PVC plates, PVC pipes, PVC profiled materials, PVC containers, children's toys, and the like.

In some preferred embodiments, the resin product of the present invention can be a product used in the medical field, for example, a Luer connector, an indwelling needle, a specimen container, a drip set, and the like.

Example

The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.

<Evaluation method>

The composition ratio of each structural unit of the rigid vinyl chloride copolymer, the number-average molecular weight and molecular weight distribution (PDI) of the copolymer, mechanical properties, self-plasticizing properties, migration resistance, and biological properties were determined by the following methods.

(copolymer composition ratio)

The copolymer composition ratio was measured by Bruker AV400 nuclear magnetic resonance instrument (THF-d8 is the solvent).

(Number average molecular weight and molecular weight distribution (PDI) of the copolymer)

The number-average molecular weight and molecular weight distribution of the copolymer are determined by Waters-1515 gel chromatography, using THF as the eluent and polystyrene as the standard.

(Mechanical behavior)

Mix 100 parts of vinyl chloride-based copolymers and 2 parts of mercaptan methyl tin heat stabilizer in each embodiment and comparative example with a twin-roll mixer, and then carry out hot pressing at 175° C. for 5 minutes and cooling for 5 minutes. Press to get a sample. The prepared samples were cut into dumbbell-shaped specimens, and the tensile strength and elongation at break were measured according to GB/T 1040-2006.

(self-plasticizing)

Self-plasticity was evaluated by glass transition temperature. Samples were prepared in the same manner as in the above evaluation of mechanical properties. The obtained samples were cut into strips with a width of 5 mm and a length of 75 mm, and were tested with DMTA 2980. The test mode was tensile mode, the frequency of test conditions was 1 Hz, and the temperature range was -60°C to 100°C.

(resistance to emigration)

In the present invention, the evaluation of the migration resistance takes into account whether there is a molecular chain in the vinyl chloride-based copolymer that is easy to migrate due to the introduction of a plasticizing segment into the molecular chain.

Samples were obtained from the vinyl chloride copolymers of each example and comparative example according to the sample preparation method in the evaluation of mechanical properties, and then each sample was cut into 2 groups in parallel, 5 small pieces in each group, weighed and recorded. The two groups of cut samples were respectively immersed in ethanol and water, soaked at room temperature for 48 hours, and finally taken out and placed in an oven at 50°C for 24 hours and then weighed. Calculate the percentage of the mass difference before and after immersion (in ethanol or water) of the sample block to the mass of the sample block before immersion, and define the average value of this percentage as the migration rate. It should be noted that the move-out rate should be ≤0.1%.

(biological)

Samples were prepared in the same manner as in the above evaluation of mechanical properties. The samples were tested for hemolysis and cytotoxicity according to GB/T 16886.5 and GB/T16886.12.

It should be noted that the value of hemolysis rate requires R<5% in GB/T 16886.5 and GB/T16886.12. In the present invention, 2.5%<R<5% is defined as good, 0.5%<R<2.5% is defined as excellent, and R<0.5% is defined as optimum.

<Example 1>

In a stainless steel micro-reactor with an internal volume of 200ml of stirring blades, 100g of deionized water, 10.4g of 2 mass % PVA aqueous solution, 0.042g of hydroxypropylmethylcellulose, 0.05g of azobisisobutyronitrile, 1.62 g of polypropylene glycol monomethacrylate with a molecular weight of 375 (PPGMA-375, the case where x=5 in formula (1)) was filled with nitrogen for 5 minutes to replace the air in the reaction vessel. Then, 52.38 g of VC monomer was introduced into the reactor. After pre-stirring for 60 minutes, the temperature was raised to 70°C to start polymerization. It should be noted that the monomer feeding mass ratio VC:PPGMA-375=97:3, and the polymerization reaction time was 8 hours. After the polymerization reaction was completed, unreacted VC monomer was reclaimed, and the polymerization product was alternately washed with a large amount of deionized water and ethanol to obtain 50.5 g of the vinyl chloride copolymer of white solid particles, and its composition: relative to the total amount of the vinyl chloride copolymer The mass, the content of the structural unit (a) was 97.5% by mass, and the content of the structural unit (b) was 2.5% by mass.

<Example 2>

Change the feed mass ratio of VC and PPGMA-375 to be VC:PPGMA-375=95:5 and the polymerization reaction time is 7.5 hours, except that, in the same manner as in Example 1, obtain the vinyl chloride copolymerization of white solid particles 51.2 g of the product, the composition: the content of the structural unit (a) was 96.4% by mass and the content of the structural unit (b) was 3.6% by mass based on the total mass of the vinyl chloride-based copolymer.

<Example 3>

Change the feed mass ratio of VC and PPGMA-375 to be VC:PPGMA-375=90:10 and the polymerization reaction time is 7.5 hours, except that, obtain the vinyl chloride series copolymerization of white solid particles in the same manner as in Example 1 49.5 g of the product, the composition: the content of the structural unit (a) was 88.2% by mass, and the content of the structural unit (b) was 11.8% by mass based on the total mass of the vinyl chloride-based copolymer.

<Example 4>

Change the feed mass ratio of VC and PPGMA-375 to be VC:PPGMA-375=80:20 and the polymerization reaction time is 8.2 hours, except that, in the same way as in Example 1, obtain the vinyl chloride copolymerization of white solid particles 47.8 g of the product, the composition: the content of the structural unit (a) was 82.1% by mass, and the content of the structural unit (b) was 17.9% by mass based on the total mass of the vinyl chloride-based copolymer.

<Example 5>

Copolymerize butyl acrylate (BA), PPGMA-375 and VC as the source of the structural unit (c), and put 100 g of deionized water and 10.4 g of PVA into a stainless steel micro-reactor with a stirring blade of 200 ml 2% by mass aqueous solution, 0.042g hydroxypropyl methylcellulose, 0.05g azobisisobutyronitrile, 5.4g PPGMA-375, 5.4g BA, and nitrogen inflated for 5 minutes to replace the air in the reactor. Then, 43.2 g of VC monomers were introduced into the reactor. After pre-stirring at room temperature for 60 minutes, the temperature was raised to 70°C to start polymerization. It should be noted that the mass ratio of monomers VC:PPGMA-375:BA=80:10:10, and the polymerization reaction time was 8 hours. After the polymerization reaction was completed, unreacted VC monomers were reclaimed, and the polymerization product was washed alternately with a large amount of deionized water and ethanol to obtain 51.5 g of vinyl chloride copolymers of white solid particles. In terms of mass, the content of the structural unit (a) was 82.1% by mass, the content of the structural unit (b) was 11.9% by mass, and the content of the structural unit (c) was 6.0% by mass.

<Example 6>

Change the mass feed ratio of VC, PPGMA-375 and BA to be VC:PPGMA-375:BA=80:2:18 and the polymerization reaction time is 8.6 hours, except that, obtain white solid in the same way as Example 5 Granular vinyl chloride copolymer 51.7, its composition: relative to the total mass of the vinyl chloride copolymer, the content of the structural unit (a) is 82.5% by mass, the content of the structural unit (b) is 2.3% by mass, and the structural unit ( The content of c) was 15.2% by mass.

<Example 7>

Change the mass feed ratio of VC, PPGMA-375 and BA to be VC:PPGMA-375:BA=80:5:15 and the polymerization reaction time is 8.6 hours, except that, obtain white solid in the same manner as Example 5 49.2 g of granular vinyl chloride copolymers, the composition of which is 82.2% by mass of the structural unit (a), 4.0% by mass of the structural unit (b), based on the total mass of the vinyl chloride copolymer, and 4.0% by mass of the structural unit The content of (c) was 13.8% by mass.

<Embodiment 8>

Change the mass feed ratio of VC, PPGMA-375 and BA to be VC:PPGMA-375:BA=80:15:5 and the polymerization reaction time is 9 hours, except that, obtain white solid in the same manner as Example 5 48.3 g of granular vinyl chloride copolymers, the composition of which is 81.8% by mass of the structural unit (a) and 16.5% by mass of the structural unit (b) relative to the total mass of the vinyl chloride copolymer. The content of (c) was 1.7% by mass.

<Example 9>

Change the mass feed ratio VC of VC, PPGMA-375 and BA VC:PPGMA-375:BA=90:5:5 and the polymerization reaction time is 8.6 hours, except that, obtain white solid particle in the same way as Example 5 52.5g of the vinyl chloride copolymer, its composition: relative to the total mass of the vinyl chloride copolymer, the content of the structural unit (a) is 88.8% by mass, the content of the structural unit (b) is 6.9% by mass, the structural unit ( The content of c) was 4.3% by mass.

<Example 10>

Change the mass feed ratio VC of VC, PPGMA-375 and BA VC:PPGMA-375:BA=90:3:7 and the polymerization reaction time is 8.6 hours, except that, obtain white solid particle in the same way as Example 5 52.9g of the vinyl chloride copolymer, its composition: relative to the gross mass of the vinyl chloride copolymer, the content of the structural unit (a) is 89.2% by mass, the content of the structural unit (b) is 3.2% by mass, the structural unit ( The content of c) was 7.6% by mass.

<Example 11>

Change the mass feed ratio of VC, PPGMA-375 and BA VC:PPGMA-375:BA=90:1:9 and the polymerization reaction time is 8.6 hours, except that, obtain white solid particles in the same manner as in Example 5 53.1g of the vinyl chloride copolymer, its composition: relative to the total mass of the vinyl chloride copolymer, the content of the structural unit (a) is 88.6% by mass, the content of the structural unit (b) is 1.2% by mass, the structural unit ( The content of c) was 10.2% by mass.

<Example 12>

Except that PPGMA-375 was replaced with polyethylene glycol monomethacrylate (PEGMA-475, in the case of x=9 in formula (1)), chlorine was obtained as a white solid particle in the same manner as in Example 5. Vinyl copolymer 50.3g, its composition: With respect to the gross mass of vinyl chloride copolymer, the content of structural unit (a) is 82.2 mass %, the content of structural unit (b) is 9.9 mass %, structural unit (c) The content is 7.9% by mass.

<Comparative example 1>

PPGMA-375 is changed into methoxyethyl methacrylate (MOEMA), the mass ratio of VC and MOEMA is VC:MOEMA=90:10 and the polymerization reaction time is 8.3 hours, in addition, with embodiment 1 In the same manner, 51.5 g of a vinyl chloride-based copolymer of white solid particles was obtained, and its composition: relative to the total mass of the vinyl chloride-based copolymer, the content of the structural unit (a) was 91.7% by mass, and the content of the structural unit based on MOEMA It is 8.3% by mass.

In addition, in Table 2, although the MOEMA-based structural unit does not satisfy the structural unit (b) of the present invention, for the purpose of convenience, the MOEMA-based structural unit is also marked as the structural unit (b).

<Comparative example 2>

Without using PPGMA-375, the mass ratio of VC to BA is VC:BA=90:10 and the polymerization reaction time is 8.0 hours, except that, in the same manner as in Example 5, a vinyl chloride-based vinyl chloride compound with white solid particles was obtained. 52.3 g of the copolymer, the composition: the content of the structural unit (a) is 90.6% by mass, and the content of the structural unit (c) is 9.4% by mass based on the total mass of the vinyl chloride-based copolymer.

<Comparative example 3>

It is polypropylene glycol monomethacrylate (PPGMA-1500) that PPGMA-375 is changed into molecular weight 1500, the feed mass ratio of VC and PPGMA-1500 VC:PPGMA-1500=90:10 and the polymerization reaction time is 8.2 hours, except In addition, 50.9 g of a vinyl chloride-based copolymer of white solid particles was obtained in the same manner as in Example 1, and its composition: the content of the structural unit (a) was 94.6% by mass relative to the total mass of the vinyl chloride-based copolymer. , the content of the structural unit based on PPGMA-1500 was 5.4% by mass.

In addition, in Table 2, although the structural unit based on PPGMA-1500 does not satisfy the structural unit (b) of the present invention, the structural unit based on PPGMA-1500 is also marked as the structural unit (b) for the purpose of convenience.

<Comparative example 4>

Change the mass feed ratio of VC, PPGMA-375 and BA VC:PPGMA-375:BA=70:5:25 and the polymerization reaction time is 8 hours, except that, obtain white solid particles in the same manner as in Example 5 51.5g of the vinyl chloride copolymer, its composition: relative to the gross mass of the vinyl chloride copolymer, the content of the structural unit (a) is 68.8% by mass, the content of the structural unit (b) is 5.3% by mass, the structural unit ( The content of c) was 25.9% by mass.

In each of the above-mentioned examples and comparative examples, the composition of the monomers participating in the polymerization is different. In order to make the reaction as complete as possible, the polymerization reaction time varies depending on the monomer composition.

From the results in Table 1 and Table 2, it can be seen that the vinyl chloride copolymers obtained in the various examples that meet the requirements of the present invention meet the conventional requirements for rigid PVC, and have excellent self-plasticizing properties, mechanical properties, and migration resistance. sexual, biological. In addition, according to visual observation, the transparency of the samples made from the copolymers obtained in Examples 1-10 and 12 was excellent; but the samples made from the copolymers obtained in Example 11 were due to the structural unit (b) The lower the content, the lower the transparency, which limits its application in fields requiring transparency.

In addition, suspension polymerization products with good morphology can be obtained in each embodiment of the present invention, that is, the vinyl chloride copolymer of the present invention can be obtained by conventional industrial techniques.

From the comparison between Example 1 and Comparative Examples 1 and 3, it can be seen that in Comparative Example 1, due to the poor copolymerization of MOEMA and vinyl chloride, there is a molecular chain of PMOEMA as a homopolymer in the copolymer resin, so there is a small amount of PMOEMA in ethanol. move out. At the same time, since MOEMA is a small molecular monomer, the self-plasticizing performance of the resulting product is reduced. In Comparative Example 3, PPGMA-1500 has poor copolymerizability with vinyl chloride due to the large number of repeating units x, and the resulting product is partially agglomerated, showing two glass transition temperatures in the Tg result.

From the comparison between Examples 9, 10, 11 and Comparative Example 2, it can be seen that in Comparative Example 2, the elongation at break of the obtained resin is low, and the self-plasticizing effect is not enough; in addition, compared with Example 11, by comparing The transparency of the samples made of the copolymer obtained in Example 2 was even worse.

From the comparison between Examples 1-11 and Comparative Example 4, it can be seen that in Comparative Example 4, the total content of structural unit (b) and structural unit (c) is greater than the scope of the present invention, and the elongation at break of the resulting resin exceeds 140 %, the tensile strength is less than 30MPa, and the Tg is also lower than 40°C, which does not meet the technical indicators of rigid PVC.

It should be noted that since the vinyl chloride-based copolymers obtained in Comparative Examples 1 to 3 had poor self-plasticization and/or mechanical properties, no biological evaluation was performed. This is because it is necessary to add expensive non-biologically toxic plasticizers to these resins during processing, so that they can be used in the medical field. However, this is not the desired technical effect of the present application.

Table 1

Table 2

Note: In Table 2, in Comparative Example 1, the amount marked by "(b)" is the amount of structural units based on MOEMA; in Comparative Example 3, the amount marked by "(b)" is based on PPGMA-1500 The amount of structural units. In Comparative Example 4, the hardness of the obtained sample is too small to be suitable for the Shore D hardness test, so the hardness value is Shore A hardness.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only examples of the present invention and are not intended to limit the present invention. Within the principle and spirit of the present invention, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the present invention.

Claims (9)

1. A rigid vinyl chloride copolymer, characterized in that, 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 monomer based on the following The structural unit (c) of the monomer represented by formula (2), CH ₂ =CR ₁ COO(R ₂ O) _x R ₃ (1) In the formula (1), R ₁ is selected from hydrogen and a linear or branched alkyl group with a carbon number of 1 to 6; the number of repeating units x is an integer selected from 2 to 20, and each R ₂ is selected from The straight-chain or branched-chain alkylene groups with 2 to 10 carbons can be the same or different; _R3 are selected from hydrogen and straight-chain or branched alkyls with 1 to 4 carbons, CH ₂ =CR ₄ COOR ₅ (2) In the formula (2), R _is selected from hydrogen and methyl, and _R is selected from straight-chain or branched alkyl with 1 to 18 carbons, straight-chain or branched with 1 to 18 carbons. Branched hydroxyalkyl, straight or branched alkoxyalkyl with 1 to 18 carbons, straight or branched aminoalkyl with 1 to 18 carbons, Or a cycloalkyl group with 3 to 18 atoms without heteroatoms; Relative to the total mass of the rigid vinyl chloride copolymer, the total content of the structural unit (b) and the structural unit (c) is 2 to 20% by mass, and the content of the structural unit (b) is 2 to 15% by mass, The content of the structural unit (c) is 1 to 18% by mass; The sum of the content of each structural unit in the rigid vinyl chloride copolymer is 100% by mass; The tensile elongation at break of the rigid vinyl chloride copolymer is 140% or less. 2. The rigid vinyl chloride copolymer according to claim 1, wherein the content of the structural unit (b) is 2.5 to 12% by mass relative to the total mass of the rigid vinyl chloride copolymer. 3. according to claim 1 and 2 described rigid vinyl chloride copolymers, it is characterized in that, with respect to the gross mass of described rigid vinyl chloride copolymers, the content of structural unit (c) is 2～17 mass %. 4. according to claim 1 and 2 described rigid vinyl chloride copolymers, it is characterized in that, in described formula (1), R ₁ is selected from hydrogen and carbon number and is 1～4 linear or branched chain The alkyl group of shape; The number of repeating units x is an integer selected from 2 to 15, and _each R is selected from a linear or branched alkylene group with a carbon number of 2 to 6, which may be the same or different. 5. The rigid vinyl chloride copolymer according to claim 1 or 2, characterized in that the rigid vinyl chloride copolymer has only one glass transition temperature. 6. The rigid vinyl chloride copolymer according to claim 1 or 2, characterized in that the number average molecular weight of the rigid vinyl chloride copolymer is 40,000-250,000. 7. A method for preparing the rigid vinyl chloride copolymer according to any one of claims 1 to 6, characterized in that it comprises: comprising vinyl chloride, the monomer shown in the formula (1) A copolymerization reaction is carried out with the raw material of the monomer represented by said formula (2). 8. A vinyl chloride resin composition, characterized in that it comprises the rigid vinyl chloride copolymer according to any one of claims 1 to 6. 9. A resin product, characterized in that it is made of the vinyl chloride-based resin composition according to claim 8.