KR100714094B1 - Stabilization of Polybutadiene Compositions and Polybutadiene - Google Patents

Abstract

The present invention is polybutadiene; Acrylate group-containing phenolic antioxidant of Formula 1; Specific phenolic antioxidants free of acrylate groups; And optionally, a polybutadiene composition comprising a phosphorus antioxidant, a sulfur antioxidant, a stabilizer other than an antioxidant, a functionalizing agent, and the like; Such polybutadiene compositions are not only stable to thermal degradation in the absence of oxygen but also to oxidative degradation in the presence of oxygen such as in air and the like.

[Formula 1]

In Formula 1 above,

R ¹ and R ² are the same as or different from each other, and are a hydrogen atom or a methyl group.

Description

Polybutadiene Composition and Method of Stabilization of Polybutadiene

The present invention relates to a polybutadiene composition. More specifically, the present invention relates to butadiene compositions comprising certain acrylate group containing phenolic antioxidants and acrylate group free phenolic antioxidants.

It is known that polybutadiene is degraded by the action of heat or oxygen during the production, processing and storage of the manufactured product. In order to prevent thermal and oxidative deterioration of such polybutadiene, polybutadiene compositions incorporating various thermal or oxidative deterioration inhibitors have been proposed.

For example, polybutadiene composition containing 2-tert-butyl-6- (tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di- Polybutadiene compositions containing tert-amyl-6- [1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and the like have been proposed. It is also known that the latter composition exhibits better deterioration inhibiting performance than the former composition (JP-A-1-168643).

Further, 2,4-di-tert-amyl-6- [1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate; And n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 3,9-bis (2- (3- (tert-butyl-4- Phenolic antioxidant without acrylate group, such as hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-detraoxaspiro [5,5] undecane A composition containing was proposed as a composition having excellent deterioration inhibiting performance (JP-A-4-100837).

However, these butadiene compositions are not satisfactory in their thermal and oxidative deterioration inhibiting performance. Accordingly, there is a need for polybutadiene compositions with good thermal and oxidative deterioration inhibiting performance.

Under these circumstances, the inventors have conducted extensive research to develop polybutadiene compositions having excellent thermal and oxidative deterioration inhibiting performance. As a result, the inventors have so far found a polybutadiene composition containing a specific acrylate group-containing phenolic antioxidant and an acrylate group-free phenolic antioxidant characterized by having a methyl group in the para position of the panol. It has been found to have significant thermal and oxidative deterioration inhibiting performance. This completes the present invention.

The present invention is polybutadiene; Acrylate group-containing phenolic antioxidant of Formula 1; An acrylate group-free phenolic antioxidant selected from the group consisting of a compound of Formula 2 and a compound of Formula 3; And, if necessary, a polybutadiene composition comprising a phosphorus antioxidant, a sulfur antioxidant, a stabilizer other than an antioxidant, a functionalizing agent, and the like.

Formula 1

[Formula 2]

[Formula 3]

In the above formula 1 to 3,

R ¹ and R ² are the same as or different from each other, are a hydrogen atom or a methyl group,

R ³ is an alkyl group having 1 to 8 carbon atoms,

n is an integer from 1 to 4,

X is an n-valent alcohol residue having 1 to 18 carbon atoms which may have a hetero atom and / or a cyclic group,

R ⁴ is an alkyl group having 1 to 8 carbon atoms,

R ⁵ and R ⁶ are the same as or different from each other, an alkyl group having 1 to 18 carbon atoms which may be a hydrogen atom or a hetero atom,

m is an integer of 1 to 3,

Y is m- is a group, and when m is 1, Y is a C1-C18 alkyl group which may be a hydrogen atom or a hetero atom, and when m is 2, Y is a sulfur atom, an oxygen atom or C1-C4 And m is 3, Y is 1,3,5-trimethylbenzene-2,4,6-trimethylene group.

Substituents R ¹ and R ² for the phenolic antioxidant of the formula (1) are the same or different from each other, are hydrogen atoms or methyl groups, preferably hydrogen atoms. It is particularly preferable that both R ¹ and R ² are hydrogen atoms and C ₄ H ₉ on the phenol ring of the phenolic antioxidant of formula 1 is a tertiary butyl group.

The phenolic antioxidant of Formula 1 is typically used in the range of about 0.005 to 1.5 parts by weight based on 100 parts by weight of polybutadiene. Preferably, it is used in the range of about 0.01 to 0.5 parts by weight.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³ in formula (2) include straight, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, tert-amyl , Tert-octyl, cyclohexyl and 1-methylcyclohexyl. Of these, methyl and tert-butyl are preferred.

An n-valent alcohol residue having 1 to 18 carbon atoms represented by X refers to the residue of an alcohol formed by removing OH. Examples of heteroatoms that n- can be included in the alcohol residue include oxygen atoms, nitrogen atoms and sulfur atoms. Examples of cyclic groups in which n- can be included in the alcohol moiety include 2,4,8,10-tetraoxaspiro [5.5] undecane ring, benzene ring and cyclohexane ring.

Representative examples of X include monohydric alcohol residues such as methyl alcohol, ethyl alcohol, 2-ethylhexyl alcohol, octyl alcohol and octadecyl alcohol; Ethylene glycol, triethylene glycol, 2,2'-thiodiethanol and 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] Dihydric alcohol residues such as cannes; Trihydric alcohol residues such as glycerol; And tetrahydric alcohol residues such as pentaerythritol.

Representative examples of the phenolic antioxidant of Formula 2 include n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol Bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate) and tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyphenyl) prop Cypionate) methane. Among them, n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis (2- (3- (tert-butyl-) 4-hydroxy-5-methylphenyl) propionyloxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis (methylene (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate) methane is preferred.

Examples of the alkyl group represented by R ⁴ in formula (3) include straight, branched and cyclic alkyl groups similar to those described above. Preferably it is methyl or tert-butyl.

R ⁵ and R ^{6, which} are the same as or different from each other, are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a hetero atom. Examples of alkyl groups as R ⁵ and R ⁶ are the straight, branched and cyclic alkyl groups similar to those described above, as well as octylthiomethylene, 2-ethylhexylthiomethylene and N, N'-dimethylaminomethylene.

Y is m- is a group, and when m is 1, Y is a C1-C18 alkyl group which may be a hydrogen atom or a hetero atom, and when m is 2, Y is a sulfur atom, an oxygen atom or C1-C4 Is m is 3, Y is isocyanuric acid-N, N ', N' '-trimethylene group or 1,3,5-trimethylbenzene-2,4,6-trimethylene group . Examples of alkyl groups having 1 to 18 carbon atoms which may optionally have heteroatoms include alkyl groups similar to those described above. Examples of alkylidene groups having 1 to 4 carbon atoms include methylene, ethylylene, propylidene and butylidene.

It is preferable that Y is a hydrogen atom, a methylene group, a butylene group, a sulfur atom or a 1,3,5-trimethylbenzene-2,4,6-trimethylene group.

Representative examples of the phenolic antioxidant of Formula 3 include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri -Tert-butylphenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2 ' Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (6-cyclohexyl-4-methylphenol), 2,2'-methylenebis (4,6-di- Tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,4-bis ( (Octylthio) methyl) -o-cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and 1,3,5-trimethyl-2,4,6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene. Among them, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol) and 2,4-bis ((octylthio) methyl) -o-cresol are preferred.

Such phenolic antioxidants are typically used in the range of about 0.01 to 1.5 parts by weight based on 100 parts by weight of polybutadiene. Preferably, it is used in the range of about 0.05 to 0.5 parts by weight.

Moreover, the polybutadiene composition of this invention can contain a phosphorus antioxidant, sulfur antioxidant, etc. further as needed.

As the phosphorus antioxidant, phosphite or phosphonite having a molecular weight of 400 or more is usually used.

Representative examples of phosphites include tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (mixed mono / dinonylphenyl) phosphite, bis (2,4,6 -Tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 2,4,6-tri-tert-butylphenyl 2- Butyl-2-ethyl-1,3-propanediol phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, distearyl pentaerythritol diphosphite, 2,2 '- Methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5- Tert-butylphenyl) -propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine and 2,4,8,10-tetra-t-butyl-6- {2- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -ethoxy} -dibenzo [d, f] [1,3,2] dioxaphosphine, It is not specifically limited to this.

Representative examples of phosphonites include, but are not limited to, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite.

As sulfur antioxidants, those having thiopropionate groups are commonly used. Examples thereof include dilauryl 3,3 '-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristyl 3,3 '-thiodipropionate, distearyl 3,3 '-Thiodipropionate, lauryl stearyl 3,3'-thiodipropionate and pentaerythritol (3-laurylthiopropionate), although not particularly limited thereto.

When used, the amount of phosphorus antioxidant and / or sulfur antioxidant is typically in the range of about 0.01 to 1 part by weight, based on 100 parts by weight of polybutadiene.

In addition, in the present invention, stabilizers other than antioxidants, functionalizing agents and the like can be used as necessary as long as they do not adversely affect the object of the present invention. Examples of such stabilizers and functionalizing agents include, but are not limited to, light stabilizers, heavy metal deactivators, flame retardants, antistatic agents, lubricants, nucleating agents, purifiers, pigments, colorants, inorganic fillers, carbon blacks, antifoams, and modifiers. Does not.

Examples of light stabilizers include hindered piperidine light stabilizers such as low molecular weight type, high molecular weight type, oligomer type and the like; Ultraviolet absorbers such as benzotriazole, benzophenone, benzoate, cyanoacrylate or triazine; And quenching agents.

Examples of polybutadienes commonly used in the polybutadiene composition of the present invention include high-cis-polybutadiene containing at least 90% of cis-1,4-bonds prepared using Ziegler catalysts, and lithium catalysts. There is a low-cis-polybutadiene containing about 35% cis-1,4-bonds prepared using. The polybutadiene included in the polybutadiene composition of the present invention may be an oil-expanded polybutadiene prepared by adding petroleum-derived high-aromatic oil, naphthalene oil, and the like.

As the polybutadiene used in the polybutadiene composition of the present invention, a product prepared by solution-polymerizing butadiene monomer in a hydrocarbon solvent using titanium, cobalt, nickel or other Ziegler catalysts, lithium catalysts and the like is preferred.

The composition of the present invention blends polybutadiene with a phenolic antioxidant and an acrylate group-free phenolic antioxidant of formula (1) and, if necessary, a stabilizer other than phosphorus antioxidants, sulfur antioxidants, antioxidants, functionalizing agents, and the like. It is manufactured by.

These blending methods are not particularly limited as long as the method allows homogeneous blending of polybutadiene with other components. Examples of such methods include adding the components to a solution prepared by adding a reaction terminator to a solution containing a living polymer of polybutadiene; Blending the components with polybutadiene (all solvent removed therefrom) using a kneading machine such as a Banbury mixer and roll; And a method of combining the components during extraction. The reaction terminator is not particularly limited as long as it has polar groups such as hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, acid halide groups, epoxy groups and the like. Preferably, water, alkyl carboxylic acid having about 1 to 8 carbon atoms and the like are used.

The composition of the present invention may comprise other polymers. Examples of other polymers include:

(1) polyethylene, such as high density polyethylene (HD-PE), low density polyethylene (LD-PE) and linear low density polyethylene (LLDPE)

(2) polypropylene

(3) α-olefin polymer

(4) EEA (ethylene / ethyl acrylate copolymer) resin

(5) EVA (ethylene / vinyl acetate copolymer) resin

(6) polystyrenes such as polystyrene, poly (p-methylstyrene) and poly (α-methylstyrene)

(7) AS (Acrylonitrile / Styrene Copolymer) Resin

(8) ABS (acrylonitrile / butadiene / styrene copolymer) resin

(9) AAS (Specific Acrylic Rubber / Acrylonitrile / Styrene Copolymer) Resin

(10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin

(11) polyvinyl chloride, polyvinylidene chloride

(12) methacryl resin

(13) ethylene / vinyl alcohol copolymer resin

(14) fluoro resin

(15) polyacetal

(16) grafted polyphenylene ether resins and polyphenylene sulfide resins

(17) polyurethane

(18) polyamide

(19) polyethylene terephthalate and polybutylene terephthalate

(20) polycarbonate

(21) polyacrylate

(22) polysulfones, polyether ether ketones, polyether sulfones

(23) aromatic polyester resin

(24) epoxy resin

(25) diallyl phthalate prepolymer

(26) silicone resin

(27) unsaturated polyester resin

(28) acrylic-modified benzoguanamine resins

(29) Benzoguanamine / Melamine Resin

30 urea resin

(31) styrene / butadiene copolymer

(32) Butadiene / Acrylonitrile Copolymer

33 silicone rubber

(34) Epichlorohydrin Rubber

(35) acrylic rubber and

36 natural rubber.

Examples of methods for mixing them with the compositions of the present invention include rolls, Banbury mixers and methods using single or twin screw extruders.

The polybutadiene composition of the present invention is not only stable to thermal deterioration in the absence of oxygen, but also to oxidative deterioration in the presence of oxygen such as in air and the like.

Example

The invention will be described in more detail with reference to the examples, which are not intended to limit the scope of the invention.

<Mixing>

A high-cis non-stabilized polybutadiene having about 95% cis-1,4-linkages prepared using a Ziegler catalyst was added to a Benbury mixer (set temperature: 110 ° C .; rotational speed: 50 rpm; kneading duration: 3 minutes). By mixing with a stabilizer set forth in Tables 1 and 2 (in these tables, the stated values represent parts by weight based on 100 parts by weight of polybutadiene) by using 1 liter / min under a nitrogen flow rate. The kneaded rubber is extruded through a roll to obtain a sheet having a thickness of about 2 mm.

Blended ingredients

PA-1: 2-3-butyl-4-methyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate

PA-2: 2,4-di-tert-amyl-6- [1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate

AO-1: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) 1,1-dimethylethyl) -2,4,8, 10-tetraoxaspiro [5.5] Undecan

AO-2: n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

AO-3: 2,2'-methylenebis (4-methyl-6-tert-butylphenol)

AO-4: 4,4'-thiobis (3-methyl-6-tert-butylphenol)

AO-5: tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane

AO-6: 2,6-di-tert-butyl-4-methylphenol

AO-7: 2,4-bis ((octylthio) methyl) -o-cresol

P-1: tris (nonylphenyl) phosphite

S-1: Dilauryl 3,3'-thiodipropionate

Test Methods

Thermal processing stability

30 g of the sample combined with the stabilizer is charged into a Banbury mixer (under a nitrogen flow rate of 1 liter / min; test temperature: 150 ° C .; rotation speed: 10 rpm preheated for 3 minutes and then 50 rpm). Thermal processing stability is assessed by torque behavior with gelation during kneading. The results were evaluated by the time before the torque peak (gel time, minutes) and are shown in Tables 1 and 2. The longer the gelation time, the more excellent the gelling inhibiting effect appears.

Oxidation resistance

The sample combined with the stabilizer is kept hot in the gear oven (100 ° C.) for a predetermined time and then the sample is dissolved in toluene (performed by stirring at room temperature for 4 hours). The toluene solution is filtered through a 50-mesh wire net. The filter cake dried at 60 ° C. for 12 hours is weighed and the ratio of toluene-insoluble matter (ratio of gelling product) is calculated. The result was evaluated by the time (hours) until the ratio (gelling rate) of the gelling product became 10% and is shown in Tables 1 and 2. The toluene-insoluble substance is a degradation product (gelling product) of polybutadiene, and the results show that the longer the gelation rate is 10%, the better the oxidation resistance, that is, the antioxidant effect.

TABLE 1

TABLE 2a

TABLE 2b

The polybutadiene composition according to the present invention is not only stable to thermal degradation in the absence of oxygen, but also to oxidative degradation in the presence of oxygen, such as in air and the like.

Claims (6)

Polybutadiene; Acrylate group-containing phenolic antioxidant of Formula 1; Acrylate group-free phenolic antioxidants of formula (2); And a polybutadiene composition comprising a phosphorus antioxidant or a sulfur antioxidant or both. Formula 1 Formula 2 In the above formula 1 to 2, R ¹ and R ² are the same as or different from each other, are a hydrogen atom or a methyl group, R ³ is a tert-butyl group, n is an integer from 1 to 4, X is an n-valent alcohol residue having 1 to 18 carbon atoms which may have a hetero atom, a cyclic group, or both. The phenolic group-free phenolic antioxidant according to claim 1 is an n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tetrakis (methylene (3). , 5-di-tert-butyl-4-hydroxyphenyl) propionato) methane polybutadiene composition selected from the group consisting of. The amount of the phenolic antioxidant of Formula 1 is in the range of 0.005 to 1.5 parts by weight and the amount of the acrylate group-free phenolic antioxidant is 0.01 to 1.5 parts by weight based on 100 parts by weight of polybutadiene. A polybutadiene composition in the range of parts, wherein the amount of phosphorus antioxidant or sulfur antioxidant or both is 0.01 to 1 part by weight. A method for stabilizing polybutadiene, comprising combining an acrylate group-containing phenolic antioxidant of formula 1, an acrylate group-free phenolic antioxidant of formula 2, and a phosphorus antioxidant or a sulfur antioxidant or both with polybutadiene. . Formula 1 Formula 2 In the above formula 1 to 2, R ¹ and R ² are the same as or different from each other, are a hydrogen atom or a methyl group, R ³ is a tert-butyl group, n is an integer from 1 to 4, X is an n-valent alcohol residue having 1 to 18 carbon atoms which may have a hetero atom, a cyclic group, or both. The phenolic group-free phenolic antioxidant according to claim 4, wherein n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tetrakis (methylene (3) A method of stabilizing polybutadiene which is at least one compound selected from the group consisting of, 5-di-tert-butyl-4-hydroxyphenyl) propionate) methane. The amount of the phenolic antioxidant of Formula 1 is in the range of 0.005 to 1.5 parts by weight, and the amount of the acrylate group-free phenolic antioxidant is 0.01 to 1.5 parts by weight based on 100 parts by weight of polybutadiene. A method of stabilizing polybutadiene in the range of parts, wherein the amount of phosphorus antioxidant or sulfur antioxidant or both is 0.01 to 1 part by weight.