JPH0364363A - Stabilizer for synthetic resin and stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a stabilizer for synthetic resins having an improved effect of improving the thermal deterioration resistance and weather resistance of a synthetic resin and the oxidation resistance in the MFR test by using a specified phosphite derivative as an effective component. CONSTITUTION:The title stabilizer is obtained by mixing a phosphite derivative of the formula (wherein R is a 4-22C hydrocarbon group; X is O or NH; and (n) and (m) are each 1-3) with optionally a phenolic stabilizer, a sulfurous antioxidant, a UV absorber, a light stabilizer, a phosphorous antioxidant, a metal deactivator, a metallic soap, a nucleator, a lubricant, an antistatic agent, a flame retardant, a pigment (dispersant), a filler, etc. The title composition is obtained by adding 0.01-5 pts.wt. (in terms of the phosphite derivative) said stabilizer to 100 pts.wt. synthetic resin, desirably a polyolefin resin.

Description

Detailed Description of the Invention (a) Purpose of the Invention The present invention relates to the stabilization of synthetic resins such as polyolefin resins, and specifically relates to stabilizers for synthetic resins and stabilized synthetic resin compositions. .

(Prior art) Various synthetic resins such as polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene, high-impact polystyrene, and ABS resins, engineering plastics such as polyacetal, polyphenylene ether, and polyamide, and polyurethane are used. It is widely used in the field of In particular, polyolefin resins are used as various molding materials such as automobile exterior materials, hollow containers, and sheet molding materials.

However, if these various synthetic resins are used as is, they will deteriorate due to the effects of heat, light, oxygen, etc. during processing or use, and their physical properties will significantly deteriorate, accompanied by phenomena such as softening, embrittlement, and discoloration. . In order to prevent the deterioration of these synthetic resins, seven or more stabilizers such as phenolic, sulfur or phosphorus antioxidants have been used in combination during the manufacturing and processing processes of synthetic resins. Added to synthetic resins.

However, conventionally used stabilizers such as antioxidants,
The stabilizing effect was not sufficient, and the synthetic resin was colored, and the stabilizer volatilized during processing at high temperatures, making it impossible to effectively demonstrate the stabilizing effect. In order to eliminate these drawbacks, combinations of several types of antioxidants have been used as described above, but satisfactorily results have not yet been obtained.

(Invention! II@) The present invention provides a stabilizer for synthetic resins that can exhibit an excellent stabilizing effect on various synthetic resins including polyolefin resins, and a stabilized synthetic resin composition. It is intended for one child.

(b) Structure of the invention (means for solving the problem) The stabilizer for synthetic resins of the present invention has the general formula % formula % (1) (wherein R is a hydrocarbon group having a carbon number of μ to 21 I-,
X is 10- or -NH-, n and m are each l
It is an integer of ~3. ) This is a stabilizer consisting of a phosphite derivative represented by:

Further, the stabilized synthetic resin composition of the present invention is a composition comprising a synthetic resin (particularly a polyolefin resin) containing a phosphite derivative represented by the above general formula (1). Further, the stabilized synthetic resin composition of the present invention is a composition containing a phosphite ester derivative represented by the above general formula (■) and various antioxidants, particularly phenolic antioxidants. .

Typical examples of the phosphite derivatives represented by Tsumugi's general formula (I) in the present invention include the following.

Tris(,2-((2-n-dodecylthio)ethylcarbonyloxy)ethyl)phosphite (hereinafter referred to as [
It is called phosphite derivative I'J. ) P(-0-CH2CH2QC-CH2CH2-8-C8
H1,) 3 tris[co((2-n-octylthio)
Tris((,2-n-dodecylthio)ethylcarboxamitomethyl)phosphite (hereinafter referred to as "phosphite derivative ■2") Acid ester derivative 1'J) Tris[λ-((2-n-dodecylthio)ethylcarboxamido)ethyl]phosphite (hereinafter referred to as "phosphite derivative I4") Stabilizer in the present invention The amount of the phosphite derivative (1) added to the synthetic resin is usually 0.07 to 5 parts by weight, preferably 0.07 to 5 parts by weight, per 100 parts by weight of the synthetic resin. θ! ~, 2 parts by weight.

In addition to the phosphite derivative (I), the stabilized synthetic resin composition of the present invention may contain various other additives as required. For example, phenolic antioxidants, sulfur-based antioxidants, ultraviolet absorbers, light stabilizers, phosphorus-based antioxidants, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, flame retardants, pigments. , a pigment dispersant, a filler, etc. can be contained. In particular, it is desirable to contain an antioxidant such as a phenolic antioxidant.

Examples of phenolic antioxidants include 2. z-
di-t-butyl-p-cresol, /, 3゜j-1 lis(j-t-butyl-≠-hydroxy-comethylphenyl)butane, ku≠'-thiobis(3-methyl-ot-t)
-butylphenol) 4I, μ'-butylidene-bis(3-methyl-6-t-butylphenol), n-octadecyl-3-(3', j'-di-t-butyl-≠I
-hydroxyphenyl)-propionate, 4-tris-(,2-methyl-≠-hydroxy-j-monobutylphenyl)butane, tetrakis[methylene-3-(3
',j/-di-t-butyl-hiro'-hydroxyphenyl)propionate comethane, /, 3. j -Tris(3,!-di-t-butylnuhydroxybenzyl)-241,6-drimethylbenzene, Tris(lIt
-t-butyl-gyrosi-methyl-3-hydroxyethyl)in cyanurate, 3. ter[bisu-ot/-dimethyl-2-(β-(3-1-butyluda-hydroxy-yo-methylphenyl)flopionyloxy)ethyl 3-2
Examples include false, Llo-tetraoxaspiro[j.j]launcan, and the like.

In addition, examples of sulfur-based antioxidants include dialkyl-based antioxidants such as dilauryl-cimilisprue and distearyl
Examples include thiodipropionate and polyhydric alcohol esters of alkyl-thiodipropionic acids such as octyl-lauryl-stearyl (eg, pentaerythritol tetralaurylthiopropionate).

In addition, ultraviolet absorbers and hindered amine light stabilizers, such as 2-hydroxy-Hiro-methoxybenzophenone, 2-hydroxy-μ-bensotriazole 1.2
(,2-hydroxy-3', !'-di-t-butylphenyl)-1-chloro-benzotriazole, 2-(,
! '-Hydroxycuj', J''-di-t-amylphenyl)benzotriazole, (2,,2'-thiobis(≠
-1-octylphenolate) cobutylamine Ni salt,
22゜ Otsu, Otsu-tetramethyl-≠-piperidinylbenzoate, bis(22, Otsu, 6-titramethyl-≠-piperidinyl) sepacate, ni(3,!-di-t-butyl≠-hydroxybenzyl) -2-n -butyl-malonate bis(/, 2,1.A-pentamethyl-≠-piperidyl), /-(λ-(3-(3,j-di-t-butyl-
hydroxyphenyl)propionyloxy)ethylni≠-(3-(3,j-di-1-butyl-hydroxyphenyl)propionyloxy)-2,1,g-tetramethylpiperidine, dimethyl succinate-/ −(,2
-Hydroxyethyl)-terthydroxyethyl 2 O, A-
Light resistance can be improved by adding a polycondensed metal such as tetramethylpiperidine.

Furthermore, weather resistance and heat resistance can also be improved by adding a phosphorous antioxidant. Examples of the phosphorus antioxidant include distearyl pentaerythritol diphosphite, tris(λ≠-di-t-butylphenyl) phosphite, tris(2-t-butyl-
≠-methylphenyl) phosphite, bis(2≠-di-
t-butylphenyl) pentaerythritol diphosphite, tetrakis (2μm di-t-7'tylphenyl)
-4t, μ'-biphenylene diphosphite, and the like.

Examples of the synthetic resin to be stabilized in the present invention include low density polyethylene, medium density polyethylene, linear low density polyethylene, polypropylene, polybutene-7
Poly-α-olefins such as ethylene-propylene random or block copolymers, poly-α-olefin copolymers such as ethylene-butene/random copolymers, poly-α-olefins such as maleic anhydride-modified polypropylene, and vinyl Copolymers of monomers, mixtures of each one of these polymers, polyvinyl chloride, methacrylic acid resins,
Polyprene, impact-resistant polystyrene, ABSm resin, A
Styrenic resins such as ES resins, polyesters such as polyethylene terephthalate and polybutylene terephthalate,
Examples include polyamide, polycarbonate, polyacetyl, polyethylene oxide, polyphenylene ether, polyurethane, and unsaturated polyester resin. In particular, polyolefin resins are preferred.

(Examples etc.) Below, phosphite derivative synthesis examples, examples, and comparative examples are given and explained in detail.

Phosphite Derivative Synthesis Example I In a four-hole flask equipped with a stirrer, a condenser, and a thermometer, n-dodecyl mercaptan, 23.0? , 2-hydroxyethyl acrylate/73y-tetra-n-butylammonium fluoride solution in tetrahydrofuran (1 mol/, 1.)2. ! -1 and anhydrous tetrahydro 7
A 100 ml run was charged, and the mixture was heated and stirred for 2 hours with jOC under a nitrogen atmosphere, and then the reaction was continued for an additional 2 hours under reflux conditions.

After the reaction was completed, tetrahydrofuran was distilled off under reduced pressure, 100 ml of toluene was added, and the mixture was washed three times with distilled water SOd. Next, after dehydration with anhydrous magnesium silicate, the solvent was removed under reduced pressure and recrystallization was performed from n-hexane to obtain (2-hydroxyethyl)-3-n-dodecylmercaptoprobionate (white crystals) 31. I got Of.

Then, in a four-bottle flask equipped with a stirrer, a condenser and a thermometer, 1 (2-hydroxyethyl)-3-n-dodecylmercaptoprobionate io, oy, pyridine 1A/? obtained by the above method was added. and anhydrous toluene SO-
was prepared, heated and stirred at 70C, and phosphorus trichloride A≠? 1
It dripped in time. After the dropwise addition was completed, the reaction was continued at 70C for another 2 hours.

After the reaction was completed, 100 ytl of toluene was added, washed three times with 100 m of distilled water, and dehydrated with fresh water magnesium sulfate. Further, the solvent was distilled off under reduced pressure and recrystallized from n-hexane to obtain the desired phosphite derivative represented by the above formula 1/0.054 (72% of theoretical amount).
Got nine. This phosphite derivative 1 was a white crystal with a melting point of 3°C, and the analytical values for each 1 were as follows.

'H-NMR absorption spectrum analysis value CCDCl3. δ (pE)m) t J70MH
z ] 0, ♂? A/g~All-ko/, j col/, A/YuJ''3 2.63~2 otori, 2.74~2.za2 44.2≠~lA, 31° (3H, t) ( /gH,m) (2H,m) (,2H,t) (2H,m) (JH,m) (DaH,m) 13C-NMR absorption spectrum analysis value (CDCl δ (ppm)) /IAO!j ' ,,22.t3,jOtsu,♂／ ,
Core 07゜2do♂j , , 29.20 , 29.2g
, 2F! 7.

3/, Zaza, 3 Yu/ri, 34L,! ,7. Otsu 3.0ri.

Otsu 3. ≠ri, /7/, 60 IR absorption spectrum analysis value (KBr (cln-') 3 2ri, 20.2g30, /7410, /≠Otsuj
.

1371, /3≠? , i, zIILo , //g
≠.

1010.10 da λ, Ta 6 Phosphite derivative synthesis example I2 According to the above synthesis example (2), a phosphite ester derivative (2) represented by the above formula was synthesized.

Synthesis Example I3 of Sonorous Acid Ester Spindle In a four-loaf flask equipped with a stirrer, a condenser, and a thermometer, n-dodecyl mercaptan, 2! ;, 01, N-methylolacrylamide/and? ? , Tetra-n-butylammonium fluoride dissolved in tetrahydrofuran 1 (
1 mol/, 8) QOml.

and 100ml of anhydrous acetone, under nitrogen atmosphere,
The mixture was heated and stirred at SOC for 2 hours, and the reaction was continued under reflux conditions for an additional 2 hours.

After the reaction, acetone was distilled off under reduced pressure and recrystallized from ethanol to obtain N-methylol-3-n-dodecumerkabutoprobioamide 26. .

? (white crystals) were obtained.

Then, the obtained &N-methylol-3-n-dodecylmercaptoprobioamide 'Z3?
, pyridine 41. oy and chloroform j3-0111
4L of phosphorus trichloride/, heated and stirred at 70C.
54 was added dropwise over 7 hours. After the completion of dripping, for another 2 hours,
The reaction was carried out at 70C.

After the reaction was completed, 00 ml of chloroform was added, washed three times with 100 ttl of distilled water, and dehydrated with anhydrous magnesium sulfate. Next, the solvent was distilled off under reduced pressure and recrystallized from n-hexane to obtain the desired phosphite derivative I3 represented by the above formula 6.9? (7.2.0% of the theoretical value
) was obtained. This derivative I5 is a white crystal with a melting point of 73.
The various analytical values were as follows.

1H-NMR absorption spectrum analysis value (CDCl, , δ (ppm), 270MH
z ]O7gza (JR, t) /, 77~/, ≠0 (/zaHm) /, 33~/, 1ptl (,2Hm)/, ≠6~
Yo! 7 (≠Hm) 2, g2 (2H, t) lA7j (jH, d) Otsu, tl-7 (/H, b) "C-NMR absorption spectrum analysis value (CDCI, δ (ppm)) /44za0 ，
2yu 1, 3, 27. Hiro≠, Jtsuj.

, 29. ．． 20, 29.3/, λZ Hiroshi, 29. j7゜3 Otsudo♂, 3.2. ≠2,3 Otsu0g3. Otsu Z77゜/
7/, 5'/IFL absorption spectrum analysis value (KBr (Tan-1)] 32riA, 301..2, Kotajμ, λri/6,
2za≠g.

/ Otsu 33. /3≠ri, /≠66, /≠Oot, /3ri/.

/3 Otsu3, /300. /2! ;7. /200. //1
0°10ri0. 7.23 Phosphite Derivative Synthesis Example ■4 Phosphite Derivative ■4 represented by the above formula was synthesized according to the above Synthesis Example +5.

Example/~≠ Comparative Example 7~≠ /3!The intrinsic viscosity measured in 5C tetralin is /,?
So, polypropylene powder with an isotactic content of 9 g% 1
00 parts by weight, various additives shown in Table 1 were blended in the proportions shown in the same table (however, in Comparative Example/, no additives were blended at all).

Each of the obtained resin compositions was heated at a cylinder temperature of 2 oC.
The mixture was melt-kneaded and granulated using an extruder having a diameter of 20 mm and L/D=20. Each pellet obtained was heated to 230C to a thickness of 0.
．． A test piece was compression molded into a J" mm sheet.

The above granulated pellets and test arm pieces were tested for heat aging resistance, weather resistance, and MFR (JIS K-673g) as described below. The results were as shown in Table 7.

■Heat aging resistance test/! ; The test piece was heated in an OC circulating air oven, and the time required for the test piece to brown and crack due to oxidative deterioration was measured.

■Weather resistance test Using an Atlas Aj/XW-WR model xenon weatherometer, the test piece was irradiated with light at a black panel temperature of OC and then bent 7 degrees. The time required for cracks to occur due to eyelidization was measured.

■MFR test MFR of granulated pellet at 230C (JISK-A'7
t♂) was measured and defined as MFR. Furthermore, the extruder was repeatedly passed through the extruder three times under the same conditions, and the resulting pellet was 230C
MFRtMFR4.

MFR is one indicator of molecular weight, and a large MFR h corresponds to a small molecular weight. Therefore, MFR+ and MFR4 are small, and MF
The small difference between FL and MF11L4 means that the drop in molecular weight due to oxidative deterioration in the extruder is small. It means big.

As is clear from Table fJg7, the polypropylene resin compositions of each example containing the stabilizer of the present invention have better heat aging resistance, weather resistance, and oxidation resistance in the MFR test than the polypropylene resin compositions of comparative examples. Degradability was significantly improved in both cases.

(C) Effects of the Invention The stabilizer of the present invention is excellent in improving the heat deterioration resistance, weather resistance, and oxidation deterioration resistance in the MFR test of synthetic resins. Furthermore, the synthetic resin composition of the present invention containing this stabilizer has excellent heat aging resistance, weather resistance, and oxidative deterioration resistance in the MFR test.

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a hydrocarbon group having 4 to 24 carbon atoms, X is -O- or -NH-, and n and m are respectively 1-3
is an integer. ) A stabilizer for synthetic resins consisting of a phosphite derivative represented by: (2) Synthetic resins have general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrocarbon group having 4 to 24 carbon atoms, X is -O- or -NH-, and n and m are 1 to 3 respectively
is an integer. ) A stabilized synthetic resin composition containing a phosphite derivative represented by: (3) Synthetic resins have general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrocarbon group having 4 to 24 carbon atoms, X is -O- or -NH-, and n and m are 1 to 3 respectively
is an integer. ) A stabilized synthetic resin composition containing a phosphite derivative represented by the following formula and a phenolic stabilizer. (4) The stabilized synthetic resin composition according to claim 2 or 3, wherein the synthetic resin is a polyolefin resin.