JPH02167322A - Heat-resistant vinyl chloride resin copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject vinyl chloride resin copolymer excellent in heat resistance, thermostability and moldability and suitable for film, sheet, etc., by graft copolymerization of an N-substituted maleimide to a vinyl chloride- based resin in the presence of a specified radically polymerizable monomer. CONSTITUTION:In producing a heat-resistant vinyl chloride-based resin copolymer by graft copolymerization of an N-substituted maleimide to a vinyl chloride- based resin, a radically polymerizable monomer (preferably methyl methacrylate, etc.) which is in the liquid state at the copolymerization temperatures, capable of dissolving the N-substituted maleimide at the copolymerization temperatures and has >=70 deg.C second-order transition temperature is used as a coexistent component in an enough amount to dissolve the N-substituted maleimide. With 100 pts.wt. vinyl chloride-based resin, preferably 1-100 pts.wt. N-substituted resin is blended and the radically polymerizable monomer is blended therewith preferably in an amount of 100-600 pts.wt. based on 100 pts.wt. N-substituted maleimide. The resultant mixture is reacted at 40-100 deg.C for 1-15hrs. by the suspension polymerization method.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat-resistant vinyl chloride resin copolymer, a heat-resistant/impact-resistant vinyl chloride resin copolymer, and a method for producing these resin copolymers. , heat-resistant vinyl chloride resin copolymers with excellent heat resistance, thermal stability, and moldability, used in films, sheets, corrugated sheets, pipes, cable ducts, decking materials, building materials, industrial products, etc., as well as impact resistance. This invention relates to excellent heat-resistant and impact-resistant vinyl chloride resin copolymers and methods for producing these resin copolymers.

(Prior Art) Vinyl chloride resin is widely used because it can be kneaded with heat and light stabilizers, plasticizers, lubricants, fillers, colorants, etc. to obtain hard, semi-hard or soft products. There is. Particularly in the field of hard materials, heat resistance has recently come to be required for molded products, and it is desired to improve the heat resistance of vinyl chloride resins.

Conventionally, as an improved heat resistance of vinyl chloride resin,
So-called post-chlorinated vinyl chloride resins, which are made by further chlorinating ordinary vinyl chloride resins, are known. However, although post-chlorinated vinyl chloride resins have improved heat resistance compared to ordinary vinyl chloride resins, they have poor thermal stability, are easily colored, and have drawbacks in mechanical moldability. Therefore, further improvement research is being conducted.

For example, IIP 1,293,542 describes the combination of an N-substituted maleimide compound and at least 5 methyl methacrylates.
A copolymer with a methacrylic acid ester monomer containing 0 weight percent or more, or a copolymer obtained by combining an N-substituted maleimide compound and another monomer that can be further copolymerized with the monomer, Thermoplastic resin compositions containing vinyl chloride polymers have been proposed.

However, this composition cannot be said to have sufficient heat resistance either.

As a subsequent improved resin, a resin made by copolymerizing vinyl chloride and N-cyclohexyl malemide has been proposed. Regarding this copolymer resin as well, in order to obtain better heat resistance, an improved manufacturing method with specified manufacturing conditions has been proposed. That is, JP-A-62-236809
As shown in the above issue, a method is known in which 3H-cyclohexylmaleimide is added in portions during copolymerization of vinyl chloride monomer and N-cyclohexylmaleimide.

However, although the vinyl chloride copolymer obtained by such a partial addition method has slightly improved heat resistance, it does not have sufficient thermal stability or impact resistance.

As mentioned above, it is possible to obtain products ranging from soft to hard as desired, is resistant to various chemicals, and has excellent heat resistance and thermal stability compared to moldable vinyl chloride resin. Furthermore, further improvements in 4JI impact resistance are desired.

[Means to solve the problem]

The present inventors have conducted extensive research to solve the above problems and have completed the present invention.

That is, the present invention provides a method for graft copolymerizing an N-substituted maleimide onto a vinyl chloride resin, in which the N-substituted maleimide is melted in a liquid at the copolymerization temperature, and the secondary transition point of the polymer is 70°C or higher. A heat-resistant vinyl chloride resin copolymer, characterized in that a radically polymerizable monomer is present in an amount sufficient to dissolve N-l-converted maleimide,
Heat-resistant and impact-resistant vinyl chloride resin copolymers and methods for producing these copolymers.

In a preferred embodiment of the heat-resistant vinyl chloride resin and the heat-resistant/impact-resistant vinyl chloride resin copolymer obtained by the method of the present invention, for example, the ratio of N-substituted maleimide to 100 parts by weight of the vinyl chloride resin is 1 to 100 parts by weight. parts by weight, and the ratio of the radical polymerizable monomer having a secondary transition point of the polymer to 1100 parts by weight of the polymer is 10 to 700 parts by weight,
It is a heat-resistant and impact-resistant vinyl chloride resin copolymer.

In another preferred embodiment, the vinyl chloride resin is obtained by graft copolymerizing vinyl chloride heptamer to rubber, and the content of rubber in the graft copolymer is 0.65 to
It is a heat-resistant and 1i impact-resistant vinyl chloride resin copolymer with a weight ratio of 20%.

Furthermore, another preferable example B is to use a vinyl chloride resin containing an antioxidant in the graft copolymerization reaction for producing the vinyl chloride resin copolymer of the present invention using a vinyl chloride resin containing rubber. This is a method for producing a heat-resistant and impact-resistant vinyl chloride resin copolymer, using it as a raw material or carrying out a graft copolymerization reaction by aqueous polymerization in the presence of an antioxidant.

The vinyl chloride resin used in the present invention is used as a backbone polymer of a heat-resistant vinyl chloride resin copolymer or a heat-resistant/impact-resistant vinyl chloride resin copolymer, and includes, for example,
Vinyl chloride homopolymer; copolymer of vinyl chloride and heptamer copolymerizable with it, i.e., α-olefins having 2 to 30 carbon atoms, acrylic acid or its esters,
Copolymerization of polyfunctional monomers such as methacrylic acid or its esters, maleic acid or its esters, vinyl compounds such as vinyl acetate, vinyl propionate, alkyl vinyl ethers, diallyl phthalate, or mixtures thereof with vinyl chloride monomer Coalescence: Ethylene/acrylic ester copolymers such as ethylene/ethyl acrylate copolymer, ethylene/methacrylic ester copolymers such as ethylene/methyl methacrylate copolymer, ethylene/vinyl acetate copolymer ([!V ^), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, polybutadiene/styrene/methyl methacrylate) (MB
S), polybutadiene/acrylonitrile/(α-methyl)styrene (ABS), styrene-butadiene copolymers, polystyrene, polymethyl methacrylate, and graft copolymers obtained by grafting vinyl chloride monomers onto mixtures thereof. These may be used alone or in combination.

Among these vinyl chloride resins, vinyl chloride homopolymer is particularly preferably used for heat-resistant vinyl chloride resin, and ethylene vinyl acetate copolymer (EV^) is particularly preferably used for heat-resistant and impact-resistant vinyl chloride resin. ), chlorinated polyethylene,
Butyl rubber, crosslinked acrylic rubber, polyurethane, polybutadiene/styrene/methyl methacrylate) (MBS
), polybutadiene/acrylonitrile/(α-methyl)styrene (ABS), styrene/butadiene copolymers, and graft copolymers in which vinyl chloride monomers are grafted onto rubbers (i.e., rubber-containing vinyl chloride copolymers). Polymer) is used.

In this case, the amount of rubber contained in the graft copolymer is
Considering the balance between heat resistance and impact resistance, preferably 0
．． 5 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 2 to IO% by weight. If the amount of rubber contained is less than 0.5% by weight, no improvement in impact resistance can be expected, and if it exceeds 20% by weight, heat resistance will deteriorate, which is not preferred.

The vinyl chloride resin used in the present invention may be produced by any of the following methods: bulk polymerization, bulk polymerization, or emulsion polymerization. Either one is fine. The degree of polymerization of these vinyl chloride resins is 300 to 5,000, preferably 400 to 3,000 for uncrosslinked vinyl chloride resins.
It is 000. Additionally, with crosslinked vinyl chloride resins, the degree of polymerization may not be measurable depending on the amount of crosslinking agent added;
Those polymerized at 0 to 80°C are preferred. If the degree of polymerization of the uncrosslinked vinyl chloride resin is less than 300, the molding holes will become brittle, and if it exceeds 5,000, the molding processability will deteriorate, which is not preferable. On the other hand, the polymerization temperature of the crosslinked vinyl chloride resin is 30
If it is less than 80"C, the molding processability will deteriorate, and if it exceeds 80"C, the molding hole will become crooked, which is not preferable.

Examples of the N-substituted maleimide used in the present invention include N-methylmaleimide, N-ethylmaleimide, N-
- Aliphatic maleimides such as n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-t-butylmaleimide, N-hexylmaleimide, N-laurylmaleimide; N-cyclohexylmaleimide, N- Alicyclic maleimide, such as bicyclo(2,2,1)butyl-2-methylmaleimide; N-phenylmaleimide, N-(o-, m- or p->hydroxyphenylmaleimide, N-(o- , m- or ρ-)
Methoxyphenylmaleimide, N-(o-, m- or p)chlorophenylmaleimide, N-(0-111- or p>carboxyphenylmaleimide, N-(o-,
m-also hap-) nitrophenylmaleimide, N-9
, 10-ethano-9,10-dihydroanthracenemaleimide, N-triphenylmethylbenzylmaleimide,
Aromatic maleimides such as N-(om or ρ-)methylphenylmaleimide are mentioned. These may be used alone or in combination.

Among these N-substituted maleimides, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(o-, m- or P-)chlorophenylmaleimide are preferably used.

In carrying out the present invention, the amount of N-substituted maleimide used is preferably 1 to 100 parts by weight, more preferably 2 to 80 parts by weight, particularly preferably 5 to 60 parts by weight, based on 100 parts by weight of the vinyl chloride resin. This is Hoshibu.

In the above quantitative ratio, if the amount of N-substituted maleimide is less than 1 part by weight, the heat resistance will not be improved sufficiently, while if it exceeds 100 parts by weight, the moldability will deteriorate and it is not suitable for practical use.

The radically polymerizable monomer used in the present invention whose second-order transition temperature is 70"C or higher means that when the monomer is radically polymerized, a radical polymerizable monomer that yields a polymer having a second-order transition temperature of 70"C or higher is used. It is a solvent monomer (hereinafter referred to as a solvent monomer).

The solvent monomer used in the present invention is: (1) liquid at the polymerization temperature at which the N-substituted maleimide is graft copolymerized onto the vinyl chloride resin, (2) the N-substituted maleimide is dissolved at that temperature, and (2) the polymer The second-order transition temperature of
It is a radically polymerizable monomer of 0'C or more.

Examples include meccrylic acid esters such as methyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, and phenyl methacrylate, styrenes such as styrene and α-methylstyrene, and unsaturated nitriles such as acrylonitrile and methacrylaterile. These may be used alone or in combination.

In particular, methyl methacrylate, L-butyl methacrylate, phenyl methacrylate, α-methylstyrene, acrylonitrile, methacrylatrile, and the like are preferably used.

These solvent monomers have a polymer secondary transition point of 7.
It can be used in combination with a monomer whose temperature is less than 0°C, but when used in combination, the composition of the mixture is determined so that the secondary transition point of the polymer in the mixture is 70°C or higher according to the following formula (1). be done.

1/Tg=W, /T, +Wz/T, 10W, /T,
→−・ ・ ・ ・ (1) Tg: Second-order transition point (°K) of the mixture polymer W,, W,, W,...: Weight fraction of specific monomer in the mixture polymer TI+ T2+ Tx...: The second-order transition point (°K) of a homopolymer made of a specific monomer In carrying out the present invention, the amount of solvent monomer used is determined to dissolve the N-substituted maleimide at the polymerization temperature at which the graft polymerization is carried out. It suffices if the criticism is sufficient.

The amount to be used may be determined by conducting a dissolution test in advance of implementation. For example, N-substituted maleimitotosi
When using cyclohexylmaleimide and methyl methacrylate as a solvent monomer, its solubility is shown in Figure 1. From this, when graft copolymerization is carried out at 80"C, for 90 parts by weight of N-cyclohexylmaleimide, It can be seen that it is sufficient to use 10 parts by weight or more of methyl methacrylate.In actual polymerization, since vinyl chloride resin is present, the N-substituted maleimide 1
10 to 700 parts by weight is suitable for 00 parts by weight,
Preferably 40 to 700 parts by weight, more preferably 10
It is 0 to 600 parts by weight. If the amount used is less than 10 parts by weight, the N-substituted maleimide cannot be dissolved and graft copolymerization cannot be carried out satisfactorily, and if it exceeds 700 parts by weight, the efficiency in improving heat resistance is poor, which is not preferable.

Examples of graft copolymerization methods applicable to the present invention include polymerization methods such as radical polymerization and radiation polymerization, and radical polymerization methods are preferably applicable.

The method for producing the graft copolymer in the present invention can be carried out by any method such as a suspension polymerization method, a bulk polymerization method, an emulsion polymerization method, or a 78-liquid polymerization method, but generally a suspension polymerization method is used. The bulk polymerization method is industrially and economically advantageous, and suspension polymerization is preferred from the viewpoint of heat removal.

As the radical initiator used in the graft copolymerization in the present invention, those commonly used in the polymerization of vinyl chloride are used, such as diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate,
Dilauryl peroxydicarbonate, Diclistyl peroxydicarbonate, Dicetyl peroxydicarbonate, Ditercythyl peroxydicarbonate, Di(ethoxyethyl)peroxydicarbonate, Di(ethoxyethyl)peroxydicarbonate, Di(ethoxyethyl)peroxydicarbonate, methoxyisopropyl) peroxydicarbonate,
di(3-methoxybutyl) peroxydicarbonate,
Di(3-methoxy-3-methylphthyl)peroxydicarbonate, di(butoxyethyl)peroxydicarbonate, di(2-isopropoxyethyl)peroxydicarbonate, dibenzylperoxydicarbonate,
Percarbonates such as dicyclohexyl peroxydicarbonate, di-tert-butyl cyclohexyl oxy-dicarbonate; tert-butyl peroxy neodecanate, amyl peroxy neodecanate, tert-octyl peroxy neodecanate,
α-1 rubberoxyneodecanate, tertiary-butyl peroxypivalate, amylveroxypivalate, tertiary-octyl peroxypivalate, α-
Recurver oxypivalate, perhexyl oxalate, ditert-butyl peroxy oxalate, acetyl cyclohexyl sulfonyl peroxide, 1
, 1,3.3-tetramethylbutyl peroxyphenoxy acetate and other peresters; diacyls such as lauroyl peroxide, diisobutyl peroxide, 2-ethylhexanoyl peroxide, 3,5.5-trimethylhexanoyl peroxide; Peroxide a; 2,2'-abbisisobutyronitrile, 2
．． 2'-azobis-2,4-dimethylvaleronitrile,
Ab compounds such as 2,2°-azobis-4-methoxy-2,4-dimethylvaleronitrile; Water-soluble peroxides such as potassium persulfate and ammonium persulfate; 2,2°-azobis(2-amidinopropane) hydro chloride,
Water-soluble azo compounds such as 2.2''-azobis(N,N'-dimethyleneisobutyramidine) hydrochloride, etc.
) may be used in combination.

The amount of radical initiator used is o, oos per 100 parts by weight of N-substituted maleimide plus solvent monomer.
20.0 parts by weight is preferred.

When carrying out the aqueous suspension polymerization method, vinyl chloride resin, N
The ratio of the total amount of the -substituted maleimide and the solvent to the amount of water is X:O, a to 1:10, preferably 1:1 to 1:4.

Q, ?If the ratio of water to the total amount of vinyl chloride resin, N-substituted maleimide and solvent monomer is less than 0.8?
The viscosity of Iu Q& increases and it tends to cause poor stirring, and 10
If it exceeds this, productivity will be low and it will be industrially and economically disadvantageous.

In suspension polymerization, suspension stabilizers may be used, such as polyvinyl alcohols, cellulose derivatives, maleic anhydride-styrene copolymers, maleic anhydride-methyl vinyl ether copolymers, polyvinylpyrrolidone, gelatin, etc. These may be used alone or in combination of two or more. Further, an emulsifier may be added as necessary.

The amount of suspension stabilizer used is 1.0 parts by weight or less, preferably 0.02 parts by weight, per 100 parts by weight of the vinyl chloride resin.
~1.0 parts by weight.

In the graft copolymerization of the present invention, chain transfer agents used in conventional methods of polymerizing vinyl polymers may be used, such as carbon tetrachloride, chloroform, methylene chloride, butyl chloride, methyl chloroform, propylene chloride or Chlorinated aliphatic hydrocarbons such as trichlorethylene;
Aromatic hydrocarbons such as toluene, xylene, methylene, cumene, ethylbenzene, L-butylbenzene or chlorobenzene; aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde or crotonaldehyde; methyl ethyl ketone, acetone, diethyl ketone, methyl isophthylatene or cyclohexanone ethyl Aliphatic or cyclic ketones such as ketones; cyclic ethers such as dioxane or tetrahydrofuran; fats such as methyl isophthylate or ethyl acetate.
Alkyl esters of ji group carboxylic acids; aliphatic alcohols such as 5ec-butyl alcohol, n-7' tyl alcohol, isobutyl alcohol or t-butyl alcohol; aliphatic carboxylic acids such as acetic acid; cyclic hydrocarbons such as methylcyclohexane, etc. Furthermore, suitably used chain transfer agents include monoalkyl mercaptans, such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, n- or t-butyl mercaptan, hexyl mercaptan, n- or t-
Hebutyl mercaptan, n- or t-octyl mercaptan, n- or t-dodecyl mercaptan, n- or L-tetradenyl mercaptan, n- or L-hexamercaptan, n- or t-bentacosyl mercaptan, 0 - or L-octacosylbutane, n
Mention may be made of mono-, di- or polymercaptans, including - or tert-triconylmerkabutane as well as mixtures thereof.

Other useful monomercaptans include thioacetic acid, 1-
Mercapto 2-butanone, methyl mercaptoacetate, ethyl mercaptothioacetate, l-mercapto-
2-ethoxyethane, diethylmercaptoethyl phosphorotrithioate, 2-mercaptoethylacetamide, dimethylactomethylmercaptan, cysteamine,
These include mercaptomethylthiopropane, monomercaptocyclohexane, hensyl mercaptan, nosteine or mercaptoethanol.

Examples of dimercaptan chain transfer agents include ethanedithiol, 2,3-dimethylcaptopropanol, and decanedithiol-1,10.

In addition, suitable polymercaptans having three or more mercaptan groups per molecule i! i! 'l'i! Taeli j Qi 1
J's sandy eyes, pentaerythritol tetra (7-mercaptoheptanoate), mercaptoacetic acid triglyceride,
Pentaerythritol tri(β-mercaptopropionate), pentaerythritol tetra(β-mercaptopropionate), cellulose tri(α-mercaptoacetate), 1,2.3-propane-trithiol,
1.2,3.4-neopentanetetrathiol, 1.2
, 3.4.5.6-mercaptopoly(ethyleneoxy)ethyl (sorbitol), 1,1.1-1-limethylbuI niapantri (α-mercaptoacetate), dipentaerythritol hexane (3-mercaptopropione- ), propane, thiopentaerythrinthotetra (α
-Mercaptoacetate), 1.6.10-) Rimerkabutocyclododecane, 1.2.3,4,5.6-
Hexamercaptocyclohexane, N, N', N', N
”-tetra(2-mercaptoethyl) viromerite amide, tri(2-mercaptoethyl)nitrilotriacetate, pentaerythritol tri(α-mercaptoacetate), pentaerythritol tetra(α-mercaptoacetate), tri(p- Mercaptomethylphenyl)
Methane, 2,2,7.7-tetrakis(mercaptomethyl)-4,5-dimercapto-octane, 5°5.5-
Examples include tri(mercaptoethyl) phosphorotrithioate and xylitpenta(β-mercaptopropionate).

Additionally, low molecular weight polymeric materials having at least three mercaptan groups per molecule include, for example, vinylthiol homopolymers and copolymers, such as polyvinylthiol. Other polymeric thiols, such as glycerol/ethylene glycol polyether borimercabutane, can also be used as chain transfer agents in the process of the invention.

These may be used alone or in combination of two or more.

The amount of chain transfer agent used in the methods of the invention is determined in large part by the particular type of chain transfer agent selected. However, in many cases, these amounts are 10 parts by weight or less per 100 parts by weight of N-11 maleide plus solvent monomer.

Generally, chain transfer agents such as mercaptans and polymercaptans in particular are the most effective and can be used at concentrations near the lower end of the above range, whereas less effective chain transfer agents, such as aromatic hydrocarbons, are used at concentrations near the upper end of the above range.

For the purpose of increasing the grafting efficiency, compounds having a swelling effect on the vinyl chloride resin, such as ketones such as acetone and methyl ethyl ketone, may be used within the range that does not impair the purpose of the present invention.

It is preferable to add an antioxidant to the graft copolymer of the present invention for the purpose of increasing thermal stability.

Examples of antioxidants that can be used include 2,6-dit
-Butyl-p-cresol (DBT), 3-t-butyl-4-hydroxyanisole (3-BIIT), 2
-t-butyl-4hydroxyanisole (3-BIIT)
), 2,2-methylenebis(4-methyl-6-t-butylphenol) (P between MB), 2,2-methylenebis(4-ethyl-6-toptylphenol) (gate B [!
BP), 4,4°-butylidene bis(3-methyl-6-
(-Butylphenol) (BBMBP), 4,4゛-
Thiobis(3-methyl-6-tert-butyl) (SBMBP), styrenated phenol, styrenated-p-cresol, 1,1.3-1-lis(2-methyl-4-hydroxy- 5t-butylphenol)butane, tetrakis[methylene-3-(3,5-di-L-butyl-4-hydroxyphenol)propionate comethane, n-octidecyl-3-(4-hydroxy-3,5
-di-savetylphenyl)propionate, triethylene glycol-bis(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate),
L3.5-)limethyl-24,6-1-lis(3,5
-di-t-butyl-4-hydroxybenzyl)benzene, 2,2°-dihydroxy-33di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, 4
．． 4-methylenebis(2,6-di-t-butylphenol), tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate, 1.3.5-)lis(
3',5'-di-t-butyl-4-hydroxybenzyl)isocyanurate, bis[2-methyl-4-(3-n
-alkylthiopropionyloxy)-5t-butylphenyl] sulfide, l-oxy-3-methylisopropyrhenzene, 2.5-dibutylhydroquinone, 2.
2'-methylenebis(4-methyl-6-tunylphenol), alkylated bisphenol, 2,5-di-t-amylhydroquinone, polybutylated bisphenol A1
Bisphenol A126-dibutyl-ρ-ethylphenol, 2,6-bis(2゛-hydroxy-3-t-
Butyl-5'-methylbenzyl)-4-methylphenol, 1,3.5-tris(4-t-butyl-3hydroxy-2,6-dimethylhenzyl)isocyanurate,
Terephthaloyrugi (2,6-dimethyl-4-t-butyl-3-hydroquinhenyl sulfide), 2,6-di-t-butylphenol, 2,6-di-t-butyl α-dimethylamino-p-cresol, 22°-methylenebis(4-methyl-6-cyclohexylphenol), hexamethylene glycol-bis(3,5-t-butyl-4-
hydroxyphenyl)propionate, 6-(4-hydroxy-3,5-di-t-butylanilino)-2,6-
Bis(octylthio)-1,3,5-)riazine, 2,
2-thio-[diethyl-bis-3-(3,5-di-t-
butyl-4-hydroxyphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyl phosphate diethyl ester, 2,4-dimethyl-6 -L-butylphenol, 4.4"-methylenebis(2,6-di-t-butylphenol), 4.4"-thiobis(2-methyl-6-
t-butylphenol), tris[β-<3,5-di-
t-Butyl-4hydroxyphenyl〉propionyloxyethyl]isocyanurate, 2,4.6-) butylphenol, bis[3,3-bis(4゛-hydroxy-3'-t-butylphenyl)butyrin acid ] Glycol ester, 4-hydroxymethyl-2,6-di-butylphenol, 4-bitroxymethyl-2,
6-di-t-butylphenol, bis(3-methyl-4
Phenolic antioxidants such as -bitroxy-5t-methylbenzyl) sulfide, N-phenyl-N"-isopropyl-p-phenylenediamine, N-phenyl-N"
・(1,3-dimethylbutyl Lp-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, 2
, 2.4-) samethyl-1,2-dihydroquinoline polymer, amine antioxidants such as diaryl p-phenylenediamine, dilauryl thiodipropionate, distearyl thiodipropionate, 2-mercaptobenzimidazole Examples include sulfur-based oxidizing soil protection agents such as phosphorus-based antioxidants such as distearyl pentaerythritol diphosphite, and the like. However, these antioxidants are not all that can be used in the present invention, and these antioxidants can be used alone or in combination of two or more kinds.

These antioxidants may be added to the obtained graft copolymer, but if they are included in the vinyl chloride resin used as a raw material or added during graft polymerization,
Thermal stability is greatly improved. When added to the polymerization gap, it may be added before or during polymerization.

The amount of antioxidant contained in the vinyl chloride resin used for graft copolymerization or added during graft polymerization is preferably 5 to 500 ppm by weight, more preferably 5 to 200 ppm by weight, particularly Preferably 5-10
It is in the range of 0 ppm by weight. If the amount of antioxidant contained in vinyl chloride resin or the amount of antioxidant added during graft polymerization is less than 5 ppm by weight, thermal stability will be insufficient, and if it exceeds 500 ppm by weight, the reaction will be inhibited. This is not preferable because it may not be completed, or even if it is completed, it will require a large amount of radical initiator and will affect the thermal stability of the resulting graft copolymer.

The reaction temperature for graft copolymerization is preferably 30 to 100
The temperature is preferably 1°C, more preferably 40 to 100°C. If the reaction temperature is less than 30"C, the reaction rate of graft copolymerization will be slow, which is industrially and economically disadvantageous;
Exceeding this will cause the vinyl chloride resin to deteriorate. The reaction temperature may be changed during the reaction, and especially when polymerization is carried out at a low temperature, the reaction temperature may be increased in the latter half in order to reduce the amount of unreacted monomer.

The reaction time is determined by the type and amount of the radical initiator used and the reaction temperature, but is preferably adjusted so that the reaction is completed in 1 to 15 hours.

The reaction vessel used for graft copolymerization is preferably a stainless steel or glass-lined autoclave equipped with a crusher and a jacket, and may be further equipped with a reflux condenser as an auxiliary heat removal device.

The atmosphere inside the reaction vessel does not contain an amount of oxygen that would adversely affect radical polymerization.

In graft copolymerization, N-substituted maleimide, solvent-based additives, radical initiators, stabilizers, chain transfer agents, swelling agents, antioxidants, etc. may be added all at once or in divided or continuous ti It can be a person.

After the graft copolymerization reaction has been completed, the slurry is dehydrated and dried after removing unreacted monomers according to a conventional method.

The graft copolymer obtained by the method of the present invention can be used as a heat and light stabilizer, a lubricant, a filler, a coloring agent, an impact modifier, a heat resistance modifier, etc., which are commonly used in the molding process of vinyl chloride resin. By blending some or all of
Normal molding processing can be performed. Furthermore, processing aids, flame retardants, smoke suppressants, and antistatic agents that are generally incorporated into vinyl chloride resins may be added to the extent that they do not impair the object of the present invention.

When molding the heat-resistant, heat-resistant/impact-resistant graft copolymer of the present invention, a wide variety of known stabilizers can be used, but the stabilizer is not limited thereto.

Examples of heat stabilizers include white lead, tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, tribasic lead maleate, lead silicate, or their silica gel coprecipitates. lead salt stabilizers; metal soaps such as magnesium soap, calcium soap, barium soap, cadmium soap, zinc soap, lead soap, tin soap; cadmium-barium type,
Liquid stabilizers such as cadmium-zinc type and barium-zinc type; organic tins such as tin alkyl sulfur compounds, tin aryl sulfur compounds, tin alkyl oxygen compounds, tin aryl oxygen compounds, organic tin carboxylic acids, and tin mercaptides. Epoxy stabilizers such as nigericidyl ethers or epoxy resins, epoxidized extract oils or alkyl esters of epoxidized natural fatty acids or resin acids, epoxy derivatives of cyclohexane; trialkyl phosphites, triphenyl phosphites, triphenyl phosphites, Organic phosphite compounds such as allyl phosphite; polyhydric alcohols,
Examples include amine compounds.

Examples of light stabilizers include salicylate esters, benzoate esters, benzophenone-based, benzotriazole-based, and acrylonitrile-based ultraviolet absorbers; ultraviolet stabilizers such as phosphorus compounds; and titanium oxide.

In addition, as a lubricant, for example, magnesium stearate, calcium stearate, barium stearate,
Metal soaps such as zinc stearate and lead stearate; hydrocarbons such as liquid paraffin, natural paraffin, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons;
Fatty acids such as stearic acid, behenic acid, araxic acid, and oxyfatty acids; Fatty acid amides such as fatty acid amides and alkylene bis fatty acid amides; Fatty acid lower alcohol esters and polyglycol esters of fatty acids; Fatty acid esters such as fatty alcohol esters of fatty acids; Examples include alcohol, polyglycol, polyglycerol, partial esters of fatty acids and polyhydric alcohols; partial esters of fatty acids and polyglycols; partial esters of fatty acids and polyglycerols.

Examples of fillers include calcium carbonate, clay, hydrated silicic acid, anhydrous silicic acid, calcium silicate, aluminum silicate, asbestos, antimony oxide, talc, aluminum trihydrate, hydrated zinc borate, magnesia, baking soda, and nitric acid. processing,
Examples include calcium hydroxide, mica, and synthetic fluorinated mica.

Examples of colorants include organic pigments such as azo lake,
Azo pigments such as insoluble azo and condensed azo, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, vat dye pigments such as anthraquinone, perylene, thioindico, and isoindoline, basic dye lakes, and acid dyes. Lake-based pigments, quinacridone-based pigments, dioxazine-based pigments, etc. are included, and inorganic pigments include precipitated pigments such as chromates, molybdates, oxides, and cyanides, oxides, and sulfides. Examples include precipitated fired pigments such as oxide-based pigments, fired pigments such as ultramarine blue and cobalt blue, metal powders, and var pigments.

Examples of impact modifiers include ethylene-vinyl acetate copolymer (EV^), chlorinated polyethylene, and ethylene-vinyl acetate copolymer (EV^).
Ethyl acrylate copolymer, ethylene-propylene copolymer (EPR), polybutadiene-acrylonitrile-styrene copolymer (8BS), polybutadiene-styrene-methyl methacrylate (MBS), polybutyl acrylate, crosslinked acrylic rubber, styrene -butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), and the like.

As a heat resistance improver, for example, acrylonitrile-α
Examples include -methylstyrene-butadiene copolymer, polymethyl methacrylate and acrylic ester copolymer, and the like.

[Function] The heat-resistant vinyl chloride resin copolymer, heat-resistant and impact-resistant vinyl chloride resin copolymer of the present invention is a blend of its constituent vinyl chloride resin and a copolymer of N-substituted maleimide/solvent monomer. Compared to other materials, it has better heat resistance.

Although its transport is not clear, by performing the graft copolymerization of the present invention, heat-resistant vinyl chloride resin copolymers, heat-resistant and impact-resistant vinyl chloride resin copolymers include vinyl chloride resin (1), A copolymer (II
), N-substituted maleimide/solvent monomer copolymer ([
It can be considered that the three components [l) exist, and that ■ acts as a polymer compatibilizer for I and ■, and I, ■, and ■ mix microscopically. When we actually measured the viscoelasticity of molded products, we found that the heat-resistant PVC resin of the present invention showed a peak pattern in which 1 and m were intertwined, or a peak pattern in which 1 and m were almost intertwined. Blends often show separated peak patterns or slightly mixed peak patterns, and differences can be seen.
Perhaps because of these differences in physical properties, the copolymer of the present invention has excellent heat resistance and high thermal stability.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but these are merely illustrative and do not limit the scope of the present invention.

In each example and comparative example, the graft copolymer 10
The following additives were added to 0 parts by weight.

Tribasic lead sulfate 2 parts by weight, dibasic lead stearate 1 part by weight, lead stearate 1 part by weight
Parts by weight, 0.5 parts by weight of stearic acid, 0.3 parts by weight of calcium stearate, and on each side, the copolymer and additives were mixed using a Henschel mixer, and the mixture was mixed with a 30 mm diameter twin-screw extruder in different directions to a thickness of 3 mm. ,
A joint board with a width of 40 mm was extruded and evaluated by the measurement method shown below.

- The softening point was measured using a load of 5 kgf according to the method of JIS K-7206.

- Thermal stability PL is the time to blacken in a gear oven at 190°C.

・For moldability, the condition of the joint plate was evaluated using the following criteria.

0 The surface is smooth and there are no sharp corners.

0 The surface is smooth and there are slight cracks on the corners.

ΔThe surface is slightly rough and there are cracks at the corners.

×The surface is not smooth and has large firmness.

The amount of antioxidant contained in the vinyl chloride resin used in the graft copolymer was determined by gas chromatography or liquid chromatography according to a conventional method.

Example-1 Bisphenol A 10 ppm by weight was placed in a stainless steel autoclave equipped with a stirrer and Jaquent with an internal volume of 840 i.
100 kg of suspension-polymerized vinyl chloride resin with a degree of polymerization of 1050 and 354 kg of deionized water were charged, and the air inside was removed using a vacuum pump to reduce the pressure.
g, azobisisobutyronitrile 0.40 kg ((N-
1 per 100 parts by weight of substituted maleimide + solvent monomer)
(parts by weight) of the mixture is aspirated and stirring is started.

Then, the mixture was reacted at 80°C for 6 hours. The reaction product was dehydrated and dried to obtain 117 kg of graft copolymer.

The obtained copolymer was extruded into a joint plate by the method described above and evaluated. The results are shown in Table 1.

Example 2 A copolymerization reaction was carried out in the same manner as in Example 1, except that a vinyl chloride resin containing no bisphenol A was used. 117 kg of copolymer was obtained. The obtained copolymer was extruded into a joint plate by the method described above and evaluated. The results are shown in Table 1.

Example 3 In Example 1, instead of the vinyl chloride resin containing 10 ppm by weight of bisphenol A, a vinyl chloride resin containing Irganox 1076, 200 ppm by weight from Ciba Geigy was used, and 4 kg of azobisisobutyronitrile was used.
A graft polymer was obtained using the same method, and a joint plate was extruded and evaluated in the same manner. The results are shown in Table 1.

Comparative example-1 Internal volume 840/! Bisphenol AIO weight p in a stainless steel autoclave equipped with a stirrer and a jacket.
P-containing suspension polymerized vinyl chloride resin (100 kg) with a degree of polymerization of 1050 was charged, the internal air was evacuated using a vacuum pump, the pressure was reduced, and 8 kg of deionized water, 10 kg of N-cyclohexylmaleimide, and 0 kg of azobisisobutyronitrile were added. .1
Aspirate 6 kg of the mixture and begin stirring. Then,
The reaction was carried out at 80°C for 6 hours. The reaction product was dehydrated and dried to obtain 107 kg of graft copolymer, which was colored yellow. The resulting copolymer was extruded into a joint plate by the method described above, but the extrusion was discontinued because it gave off a strong odor and irritated the eyes. The results are shown in Table 1.

Comparative Example-2 Bisphenol AlO polymerization without graft copolymerization
A suspension polymerized vinyl chloride resin containing fippm and having a degree of polymerization of 1050 was directly extruded and evaluated by the above-mentioned method. The results are shown in Table 1.

Comparative Example-3 310 kg of deionized water, 105 g of 70% by weight di-2-ethylhexyl peroxycarbonate) and 5 k of N-cyclohexylmaleimide were placed in a stainless steel autoclave equipped with a stirrer and jacket with an internal volume of 8401 kg.
After degassing under reduced pressure, 8.4 kg of a 5 wt% aqueous solution of partially saponified polyvinyl alcohol with a degree of saponification of 80 mol% and a degree of polymerization of about 2000 and 120 kg of vinyl chloride monomer were added, and the temperature was raised to 57°C. After 2 hours and 30 minutes of reaction, 5 kg of N-cyclohexylmaleimide was dispersed in 30 kg of deionized water in which 30 g of the partially saponified polyvinyl alcohol had been dissolved, and the mixture was pressurized into an autoclave. As the reaction progresses, the autoclave internal pressure increases to 6.5k.
g/cm"G was confirmed, the unreacted vinyl chloride nitrate was collected, and the slurry was dehydrated and dried by a conventional method to obtain 1 lok of a white powder copolymer. Example-1 Extrusion evaluation was carried out in the same manner as above.The results are shown in Table 1.

Reference Example-1 252 kg of deionized water was placed in a stainless steel autoclave equipped with an internal volume of 8,401 liters of stirrer and jacket.

12.5 kg of N-cyclohexylmaleimide, 25 g of partially saponified polyvinyl alcohol with a degree of saponification of 80 mol% and a degree of polymerization of about 2000, 150 g of lauroyl peroxide
After removing the air inside with a vacuum pump, 37.5 kg of methyl methacrylate was charged with stirring, and 8
Polymerization was carried out at 0°C. 6:01: After continuing the old 5 minute reaction,
Dehydrate and dry the slurry to produce white powder particles weighing 47゜5 kg.
I got it.

Comparative Example-4 Suspension polymerized vinyl chloride 4M with polymerization degree of 10SO in Comparative Example-2
A joint board was evaluated by extruding 1 ook of fat and 40 kg of the N-cyclohexylmaleimide/methyl methacrylate copolymer of Reference Example 1 by the method described above. The results are shown in Table 1.

Comparative Example-5 In Example-1, instead of the vinyl chloride resin containing 10 ppm by weight of bisphenol A, bisphenol A 1
A graft polymer was obtained using a vinyl chloride resin containing 00 weight ff1ppa+ and Irganox 1076500 weight ppm from Ciba Geigy and azobisisobutyronitrile lokg, and a joint plate was extruded and evaluated in the same manner. It had a strange odor and was irritating to the eyes. The results are shown in Table 1.

Examples-4 to 17 In Example-1, graft copolymers were obtained using various N-substituted-reids shown in Table 2 instead of N-cyclohexylmaleimide, and joint plates were extruded and evaluated in the same manner. did. The results are shown in Table 2.

Examples 18 to 21, Comparative Examples 6 to 7 In Example 1, the amount of N-cyclohexylmaleimide and the amount of methyl methacrylate were replaced with the amounts shown in Table 3, and azobisisobutyronitrile The total amount of N-cyclohexyl maleate and methyl methacrylate is 1
00 parts by weight, and the resulting graft copolymer was extruded and evaluated in the same manner. The results are shown in Table 3.

Examples 22 to 23, Comparative Example 8 In Example 1, the solvent monomer was changed from methyl methacrylate to those shown in Table 4, and the obtained graft copolymers were extruded and evaluated in the same manner. The results are shown in Table 4.

Examples-24 to 27, Comparative Examples-9 and 10 In Example-1, the amount of methyl methacrylate as a solvent monomer was
The amount of azobisisobutyronitrile was replaced with the amount shown in the table, and the amount of azobisisobutyronitrile was 1 part by weight per 100 parts by weight of the total amount of N-cyclohexyl maleide and methyl methacrylate, and the resulting graft copolymer was prepared in the same manner. The extrusion was evaluated. The results are shown in Table 4.

Reference example-2 (Production example of crosslinked acrylic rubber) Internal volume 5rT
2000 kg of deionized water, 7.0 kg of anionic emulsifier, 0.67 kg of ammonium persulfate, n-
700 kg of butyl acrylate and 1.31 kg of 1.3-butylene gelicol dimethacrylate were added, and after the air inside was replaced with nitrogen, polymerization was carried out at 60°C. 16 hours after the start of polymerization, the internal temperature began to rise rapidly, so heat was removed from the jacket, and the reaction continued for another 10 hours while maintaining the polymerization temperature, and the polymerization reaction was stopped. The concentration of the obtained latex was 25% by weight, and its average particle size was 0.07 μm.
Met.

Reference Example 3 (Production Example of Rubber-Containing Graft Copolymer) In a stainless steel autoclave with internal volume 71 (1 machine, Jaquent), 2700 kg of deionized water, saponification degree 80
mol%, partially saponified polyvinyl alcohol with a degree of polymerization of about 2000, 1.5 kg, methylcellulose 1.4 kg, 2
．． 2'-Azobisisobutyronitrile 0.17kg, 2
．． 2′-azobis-2,4-dimethylvaleronitrile 0
．． After removing 29 kg of vinyl chloride with a vacuum pump, 368 kg of acrylic latex (solid content: 92 kg) with a concentration of 25% by weight as shown in Reference Example-2 was charged with stirring and coagulated, and then 1400 kg of vinyl chloride was added. was charged and polymerization was carried out at 57°C. After confirming that the internal pressure of the polymerization machine had decreased to 6.5 kg/adG pressure as the reaction progressed, 25 g of bisphenol A was added to stop the polymerization reaction.

Next, after removing unreacted vinyl chloride monomer, the slurry was dehydrated and dried by constant evaporation to obtain 1282 kg of white powder particles. According to chlorine analysis, the rubber content is 7.2.
% by weight.

Reference Example-4 In Reference Example-3, 368 kg of acrylic latex (
(solid content 92 kg), vinyl acetate 45% by weight E
92 kg of VA was added after deionized water and the polymerization reaction was carried out in the same manner to obtain 1280 kg of white powder particles. According to chlorine analysis, the rubber content was 7.2% by weight.

Example-28 In Example-1, bisphenol A 10 pp by weight
A graft copolymer was obtained using the vinyl chloride resin of Reference Example 3 in place of the suspension-polymerized vinyl chloride resin containing m and having a degree of polymerization of 1050, and a joint plate was extruded and evaluated by the method described above. The results are shown in Table 5. The Charpy impact value was measured according to JIS K 6745 at 60 kgf -
This was done using a hammer with a moment of cm.

Example-29 Bisphenol A 10 weight + ftp in Example-1
A graft copolymer was obtained by using the vinyl chloride resin of Reference Example 4 in place of the suspension polymerized vinyl chloride resin containing pm and having a degree of polymerization of 1050, and a joint board was extruded by the method described above. The results are shown in Table 5.

Reference Example 5 In Reference Example 3, instead of 25 g of bisphenol A, 125 g of bisphenol A and Irganox 1076650 g of Chiha Geigy were used to terminate the polymerization reaction. 1283 kg of white powder particles were obtained. According to chlorine analysis, the rubber content was 7.2i[t%].

Comparative Example-11 Bisphenol A 10-fold ffip in Example-1
Using the vinyl chloride resin of Reference Example-5 instead of the vinyl chloride resin containing pm, azobisisobutyronitrile 1
A graft copolymer was obtained using 0 kg, and a joint board was similarly extruded and evaluated. It had a strange odor and was irritating to the eyes. The results are shown in Table 5.

Table 5 [Effects of the Invention] The heat-resistant vinyl chloride resin of the present invention has excellent heat resistance, especially Vikaft softening point, and can provide a vinyl chloride resin with excellent thermal stability and moldability, which is extremely industrially possible. Useful.

In addition, the heat-resistant and impact-resistant vinyl chloride resin produced by the method of the present invention has excellent heat resistance, especially Vikaft softening point, and is also excellent in impact resistance, as well as excellent thermal stability and processability. Extremely useful.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the solubility of N-cyclohexylmaleimide in methyl methacrylate in the present invention.

Claims (1)

[Claims] 1) A method of graft copolymerizing an N-substituted maleimide onto a vinyl chloride resin, wherein (1) the N-substituted maleimide is a liquid at the copolymerization temperature, and (2) the N-substituted maleimide is dissolved at that temperature. (3) A heat-resistant vinyl chloride resin copolymer characterized in that a radically polymerizable monomer having a polymer secondary transition point of 70° C. or higher is present in an amount sufficient to dissolve (4) N-substituted maleimide. Method of manufacturing coalescence. 2) In a method of graft copolymerizing an N-substituted maleimide to a vinyl chloride resin, (a) a rubber-containing vinyl chloride copolymer is used as the vinyl chloride resin, and (b) (
1) a radically polymerizable monomer that is liquid at the copolymerization temperature, (2) dissolves the N-substituted maleimide at that temperature, and (3) has a polymer secondary transition point of 70°C or higher;
(4) A method for producing a heat-resistant and impact-resistant vinyl chloride resin copolymer, which comprises coexisting a sufficient amount of N-substituted maleimide to dissolve it. 3) In the manufacturing method according to claim 2), the rubber content of the rubber-containing vinyl chloride copolymer is 0.5 to 1.
The method for producing a heat-resistant and impact-resistant vinyl chloride resin copolymer according to claim 2), wherein the amount is 0% by weight. 4) The method for producing a heat-resistant vinyl chloride resin copolymer according to claim 1), wherein the vinyl chloride resin contains 5 to 500 ppm of an antioxidant. 5) The method for producing a heat-resistant and impact-resistant vinyl chloride resin copolymer according to claim 2) or 3), wherein the vinyl chloride resin contains 5 to 500 ppm of an antioxidant. 6) The method for producing a heat-resistant vinyl chloride resin copolymer according to claim 1), wherein 5 to 500 ppm of an antioxidant is added to the vinyl chloride resin during the graft polymerization. 7) The method for producing a heat-resistant and impact-resistant vinyl chloride resin copolymer according to claim 2) or 3), wherein 5 to 500 ppm of an antioxidant is added to the vinyl chloride resin during the graft polymerization. 8) A method for aqueous suspension polymerization of a heat-resistant vinyl chloride resin copolymer, which is graft copolymerized in an aqueous medium in the production method of claims 1) to 7). 9) A heat-resistant vinyl chloride resin copolymer produced by the method according to claim 1), 4), 6) or 8). 10) A heat-resistant and impact-resistant vinyl chloride resin copolymer produced by the method according to claim 2), 3), 5), 7) or 8). 11) In the heat-resistant vinyl chloride resin copolymer according to claim 9), the ratio of the N-substituted maleimide to 100 parts by weight of the vinyl chloride resin is 1 to 100 parts by weight, and 100 parts by weight of the N-substituted maleimide. A heat-resistant vinyl chloride resin copolymer having a ratio of radically polymerizable monomer to 10 to 700 parts by weight. 12) In the heat-resistant and impact-resistant vinyl chloride resin copolymer according to claim 10), the ratio of the N-substituted maleimide to 100 parts by weight of the vinyl chloride resin is 1 to 100 parts by weight, and the N-substituted maleimide A heat-resistant and impact-resistant vinyl chloride resin copolymer in which the ratio of radically polymerizable monomer to 100 parts by weight is 10 to 700 parts by weight.