JPS6016456B2 - polyolefin formulation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to non-toxic stabilizing compositions of polyolefins.

Polyolefin molding is usually carried out at a temperature of 20,030 qo or higher, sometimes close to 300 qo.

At this time, the molecular weight of these polymers decreases due to chemical effects such as heat and oxygen, and mechanical effects such as shearing force, resulting in a decrease in their mechanical properties, which may significantly reduce the value of the product. many. In order to prevent such quality deterioration during molding, sterically hindered phenols such as BHT have conventionally been added as stabilizers. However, since the safety of these phenols to the human body has not been confirmed, there has been a demand for more harmless stabilizers. This demand is particularly strong in the fields of food packaging, food and medical containers, toys, etc. Although it is known that tocopherols are used as non-toxic heat stabilizers, tocopherols alone are not yet sufficiently effective.

More tocofe. 6-Hydroxychroman derivatives, which are similar to tocopherols and have been disclosed in Tokkokuki No. 49-723 and JP-A No. 49-112944, do not exhibit sufficient effects when used alone with tocopherols. As a result of intensive study to improve the above technology, the present inventor found that an excellent synergistic effect is exhibited when used in combination with the following compounds. That is, the present invention provides a polyolefin with a 6-hydroxychroman derivative (1) represented by the general formula (wherein R, , R2, R3 are hydrogen or a lower alkyl group, and R4 is a hydrocarbon group) and a glutamic acid metal salt or a 6-hydroxychroman derivative of the general formula MX Y(〇H) Matsuju 3Y-22(G)2・aH20(
In the formula, M is Mg, Ca or zinc, G is C03 or HP
04, ×, Y, Z are positive numbers, a is 0 or a positive number) This is a polyolefin blend formed by blending a compound {B} selected from the complex compounds represented by 0 or a positive number.

The polyolefins used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-
It is a homopolymer or copolymer of pentene.

In the case of a copolymer, it may contain a polyunsaturated compound such as a conjugated diene or a non-conjugated diene as a copolymerization component. Particularly suitable polyolefins are those obtained using a so-called Ziegler type catalyst consisting of a combination of a transition metal compound and an organometallic compound. These may be decalcified products or eel demineralized products. 6
- In the general formula of the hydroxychroman derivative ■, R,, R2
, R3 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, particularly a methyl group.

Moreover, as R4, CQ group, CH3C(C&)=CHC
H2CH2 group, C is [CH(CH3)CQCday2CH2
]3 groups, CH8 [C(CH3)=CHCQC2]3 groups, etc., are preferably hydrocarbon groups having 1 to 16 carbon atoms, and particularly preferably carbon hydrogen groups having 16 carbon atoms. Specifically, various tocopherols such as Q, 8, y, and 6 and mixtures thereof, 2-(4-methyl-benta-3
2,5-dimethyl substituted product, 215,8-trimethyl substituted product, 2,517 of -enyl)-16-hydroxychroman
・8-tetramethyl substituted product, 2,2,7-trimethyl-
5-rt-butyl-6-hydroxychroman, 2.2
・5-trimethyl-7, rt-butyl-6-hydroxychroman-2, 215-trimethyl-6, rt-butyl-6-hydroxychroman, 202-dimethyl-5
-te-butyl-6-hydroxychroman and the like. In the present invention, the compound used in combination with the 6-hydroxychromans is selected from glutamic acid metal salts or aluminum complex compounds represented by the above formula.

As the metal salt of glutamic acid, for example, sodium salt, potassium salt, calcium salt, etc. are used. These salts may be such that either one of the two carboxyl groups constitutes a salt, or both of the two carboxyl groups constitute a salt. Among these, glutamic acid monosodium salt is particularly preferred. In addition, as composite compounds of aluminum, Mg6Al2 (0 days), 6C03・4 days 20
, M&A12(OH)20CQ・porridge20, MgAl2
(OH), 4C03・4Q0, M&.

AI2(OH)22(C03) 214 days 20, Mg6M
2 (OH), 6HP04・4th 20, CaGAl
2(〇H), 6C. 3.'' Day 20, Z is AI2 (〇H)
,6C.

3.4&.

Alternatively, dehydrogenation of these can be mentioned. In these complex compounds, M is Mg and G is C03
Most preferred are compounds where . Component (■) is 0.005% to 0.5% by weight, especially 0.01 to 0.1% by weight, and tB} component is 0.0% by weight based on the polyolefin.
It is preferable to add 0.05 to 5% by weight, particularly 0.01 to 0.5% by weight. When polyolefin obtained by polymerization with a Ziegler type catalyst is used without deashing, it is more effective to use an alcohol or a polyhydric alcohol having an ether bond, an ester bond, or an amino bond in addition to the above two components. becomes noticeable.

Examples of such compounds include polyhydric alcohols such as glycerin and sorbitan bentaerythritol, partial esters of these polyhydric alcohols and fatty acids with 8 or 22 carbon atoms, polyethylene glycol, polypropylene glycol, citric acid mono- or distearic acid. Polyhydric alcohols without 8 carbon atoms such as ester, propylene glycol, sucrose, polyglycerin, polyethylene glycol, polypropylene glycol, polyoxyethylene glycerin, polyoxyethylene sorbitan, etc.
22 fatty acid partial esters, monoethers of polyethylene glycol and aliphatic alcohols with 12 carbon atoms or 22 carbon atoms or phenols with 4 carbon atoms or 22 alkyl groups, aliphatic amines with 8 carbon atoms and 22 carbon atoms Alternatively, N·N-bis(2-hydroxyethyl)-substituted aliphatic amide can be exemplified. These are preferably from 0.01 to 5% by weight, particularly preferably from 0.05 to 1.0% by weight, based on the polyolefin. It is preferable to mix it in a weight percent of . In the present invention, other stabilizers, such as dialkylthiodipropionic acid esters having an alkyl group of 12 to 22 carbon atoms, tetrakis[methylene-
3-(3',5-di-rt-butyl-4'-hydroxyphenyl)propionate] methane, fatty acid amide having 12 or 22 carbon atoms may be blended. Alternatively, there is no problem in adding other fillers or the like. Since the composition of the present invention exhibits excellent thermal stability and heat resistance during molding, deterioration of the polymer can be prevented.

It can also be used for food packaging, toys, etc. Hereinafter, it will be explained in more detail with reference to Examples.

Examples 1 to 19 Comparative Examples 1 to 22 Polypropylene (C
The compounds shown in Table 1 were blended into a pellet of 240 mm using an extruder.

The melt index (MI) of these pellets was measured. MI was measured according to ASTM D-1238-65T. The smaller the MI, the greater the thermal stabilization effect during molding. Spiritual desk cloud R Kame Renki L Spirit S Lord's mouth ``' H★ Toromi n recognition l mu', 0 subconnection b cold n ′′′/ Suzu'' is also available. ''y Misaki 3-inch garden 1' Ruts 03) *** Examples 20-24, Comparative Examples 23-29 Low-pressure polyethylene polymerized with Ziegler type catalyst (/
, Izex ■500 Blood manufactured by Mitsui Petrochemical Industries ■) Powder 1
00 parts by weight of the compounds listed in Table 2 were blended.

After granulating these with a granulator at 31000,
Their intrinsic viscosity was measured. [R] was determined by measuring the specific viscosity of the decalin solution at 135:00. The results are shown in Table 2. Here, the larger the value, the greater the thermal stabilization effect. Table 2 Examples 25 to 30, Comparative Examples 30 to 37 Poly 4-methyl-1-pentene (melting point 231.yo by DSC measurement, average molecular weight 73000 by light scattering method)
0) Additives were added in the amount shown in Table 3 to 100 parts by weight of the powder, and the mixture was granulated at 290q0 using a granulator.

Table 4 shows the melt index (MI) measurement results for each pellet. The skin is rated 4.0 and has excellent thermal stability.
Note that the MI measurement conditions were a temperature of 260° C. and a load of 5k9. Table 3

Claims (1)

[Claims] 1 Polyolefins include 6-hydroxychroman represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2, R_3 are hydrogen or a lower alkyl group, and R_4 is a hydrocarbon group) Derivative (A) and glutamic acid metal salt or general formula M_XAl_Y(OH)_2_X_+_3_Y_-_2
A compound (B ) is a polyolefin compound. 2. The composition according to claim 1, wherein the 6-hydroxychroman derivative (A) is tocopherol. 3. The composition according to claim 1, wherein the glutamate metal salt (B) is monosodium glutamate. 4 Compound compound (B) has the general formula Mg_XAl_Y(OH)_2_X_+_3_Y_-_
2_Z(CO_3)_Z・aH_2O (in the formula, X, Y,
2. The composition according to claim 1, wherein Z is a positive number and a is 0 or a positive number.