CA1239243A

CA1239243A - Poly-1-butene resin composition

Info

Publication number: CA1239243A
Application number: CA000427725A
Authority: CA
Inventors: Chikara Igarashi; Takashi Hashimoto
Original assignee: Mitsui Petrochemical Industries Ltd
Current assignee: Mitsui Chemicals Inc
Priority date: 1983-05-09
Filing date: 1983-05-09
Publication date: 1988-07-12

Abstract

ABSTRACT OF THE DISCLOSURE
The invention provides a cold or hot water supplying pipe capable of supplying cold or hot water containing sterilizing chlorine dissolved therein, said pipe being composed of a resin composition comprising a poly-1-butene polymer and at least one hindered phenol selected from the group consisting of (a) 3,5-di-tert-butyl-4-hydroxybenzoates of the following formula wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms;
(b) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene;
(c) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)isocyanurate;
(d) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;
(e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate;
(f) a nickel salt of a monoethyl ester of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid), (g) 2,2'-dihydroxy-3,3'-di(.alpha.-methylcyclohexyl)-5,5'-di-methyl-diphenylmethane, (h) 4,4'-thiobis(3-methyl-6-tert-butyl-phenol);

(i) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)-butane;
(j) tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate)methane; and (k) 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine.

Description

This invention relates to cold or hot water supply pipes composed of a poly-l-butene resin composition having excellen-t resistance and pressure-resistant strength against cold or hot water having sterilizing chlorine dissolved therein.
Metallic pipes such as zinc-placed steel pipes, copper pipes and lead pipes have heretofore been used as pipes for supplying cold or hot water. The steel pipes have the defect that rust is formed to generate red or black water. The copper pipes have the defect that pin holes are generated owing to electrolytic corrosion, or blue water occurs as a result of rust formation. ~lence, new piping materials have been desired. To some extent, plastic pipes such as pipes made of polyvinyl chloride, polyethylene and poly-l-butene which do not develop rust or pinholes owin~ to electrolytic corrosion have already come into practical use. In particular, poly-l-butene is now evaluated as one of the most suitable resins for water supply pipes because of its excellent pressure-resistant strength, internal pressure creep durability at high temperatures, high and low -temperature properties, abrasion resistance, and flexibility.
; 20 Like other synthetic resins, poly-l-butene also undergoes chemical degradation under the ackion of sterilizing chlorine added to city water, and tends to lose its inherent high performance. This tendency becomes especially pronounced in hot water supply pipes which are placed under high-temperature and high-pressure loads.
To the best of the knowledges of the present inventors, there has not been known a poly-l-butene resin composition having ~l~3~

excellent resistance (to be referred to as chlorine water resistance) to cold or hot water containing sterilizing chlorine dissolved therein (to be referred to as chlorine water) and excellent pressure-resistant strength.
It is an object of this invention therefore to provide a water supply pipe composed of a poly-l-butene resin composition having excellent chlorine water resistance.
Another object of this invention is to provide a water supply pipe composed of a poly-l-butene resin composition having excellent chlorine water resistance and excellent pressure resistance in the state of being in contact with chlorine water (to be referred to simply as pressure resistance).
Still another object of this invention is to provide a water supply pipe composed of a poly-l-butene resin composition which has excellent surface luster and shows only a small extent of decrease in the degree of polymerization of the poly-l-butene polymer when it is kept in contact with chlorine water for a long period of time.
A further object of this invention is to provide a water supply pipe composed of a poly-l-butene resin composition having excellent chlorine water resistance and pressure resistance which is suitable for use as a material for pipes used to supply cold or hot water having a minor amount of sterilizing chlorine dissolved therein.
Other objects and advantages of this invention will become apparent from the following description.
The invention provides a cold or hot water supplying pipe capable of supplying cold or hot water containing sterilizing ~, 2 -"'"' "1.

~'~3~

Chlorine dissolved therein, said pipe being composed of a resin composition comprising a poly~ utene polymer and at least one hindered phenol selected from the group consisting of (a) 3,5-di-tert-butyl-4-hydroxybenzoates of the following formula (CH3)3C ~ o HO ~ ~ C-O-R
(CH3)3 wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atorns;
(b) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, (c) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, (d) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, (e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, (f) a nickel salt of a monoethyl ester of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid), (g) 2~2l-dihydroxy-3l3l-di(~-methylcyclohexyl)-5t5~-di methyl-diphenylmethane, (h) 4,4'-thiobis(3-methyl-6-tert-butyl-phenol), (.i) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)-butane, (j) tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate)methane, and (k) 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine.

~3~

The resin composition of the supplying pipe according to the invention preferably further comprises at least one compound selected from the group consisting of (1) 2,6-tert-butyl-p-creosol (m) tris(2,4-di-tert-butyl-phenol) phosphite, and (n) tocopherol.
The invention also provides a method for providing a poly-l-butene resin composi-tion with chlorine water-resistance and pressure-resistance for both cold and hot water having a minor amount of sterilizing chlorine dissolved therein, said method comprising incorporating in said poly-l-butene resin composition a stabilizing effective amount of at least one hindered phenol selected from the group consisting of (a~ 3,5~di-tert-butyl-4-hydroxybenzoates of the following ~ormula (CH3~3C "
EIO ~ C-O-R

(CH3)3 wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms;
(b~ 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl~benzene, (c~ 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, (d) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, ~ e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-: propionate, (f) a nickel salt of a monoethyl ester of bis(3~5-di-tert-:~ - 3a -'``~`'

2~

butyl~4-hyd.roxybenzylphosphonic acid), (g) 2,2' dihydroxy-3,3'-di(~-methylcyclohexyl)-5,5'-di-methyl-diphenylmethane, (h) 4,4' thiobis(3-methyl-6-tert-butyl-phenol), (i) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane, (j) tetrakis(methylene-3-(3,5-di-tert-butyl-~-hydroxy-phenyl)propionate)methane, and (k) ~,4'-methylene-bis(2,6-di-tert-butyl-phenol) in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine.
The invention further provides a method for providing a poly-l-butene resin composition with chlorine water-resistance and pressure-resistance for both cold and hot water having a minor amount oE sterilizing chlorine dissolved therein, said method comprising incorporating in said poly-l-butene resin composition a stabilizing effective amount of at least one hindered phenol selected from the group consisting of (a) to (k) defined above in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine.
The hindered phenols (a) to (k) used in the present invention are compounds known as antioxidants or ultraviolet absorbers.
Investigat.ions of the present inventors have shown that while very many hindered phenols have been known heretofore, only the above-specified compounds (a) to (k) can improve the chlorine water resistance or pressure resistance of poly-l-bu-tene polymer to a fully satisfactory degree and other hindered phenols are useless for this purpose, although no clear reason has yet been .~ - 3b -i , .

~3~2~
assigned to it.
The specific structures of the hindered phenols (a) to (k) used in this invention are shown below.
(a) 3,5-Di-tert butyl-4-hydroxybenzoates These compounds are represented by the following formula (I).

:~ 3c -; i., ,;~ , ~3~2~3 _ 4 --(CH3)3c o H0 ~ C-0-R (I) (cEI~)3c wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms~
In formula (I) above, the Cl ~ C18 alkyl group may be linear or branched, and includesi for example9 methyl, ethyl~ propyl, butyl, pentyl, hexyl~ heptyl~ octyl~
nonyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl.
Examples of the C6 - C18 aryl group are phenyl, naphthyl and diphenyl or alkyl-substituted aryl groups resulting from the substitution of the above aryl groups by 1, 2 or 3 alkyl groups having 1 to 12 carbon atoms provided that the ~ total number of carbon atoms in the substituted aryl groups : does not exceed 18. Specific examples of the alkyl-sub~
stituted aryl groups are 3,5-di-tert-butylphenyl, 2,6-di-ter-t-butylphenyl, 2,4-di-tert-butylphenyl, 2l4,6-tri-tert-butylph~nyl, 2,6-dimeth~ylphenyl, and 2,6-di-tert-butyl-4-methylphenyl .hus, examples of the 3,5-di-tert-butyl-4-hydroxy-:~ 20 benzoates of formula (I) include methyl 3,5-di-tert-butyl-. 4-hydroxybenzoate, propyl 3,5-di-tert-butyl-L~-hydroxy-: benzoate, octyl 3,5-di-tert-butyl-4-hydroxybenzoate~ dodecyl

3,5-di-tert-butyl-4-hydroxybenzoate, hexadesyl 3,5-di-tert-butyl benzoate, 3,5-di-tert-butylphe~yl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,5-di-tert-butylphenyl 3,5-di-tert-butyl-

4~hydroxybenzoate, 2,4,6-tri-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,'~-di-tert-butylphenyl 3,5--di-: tert-butyl-4-hydroxybenzoate, and 2,6-dimethylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
~; ~ 30 : (b) 1,3,5-~rimethyl-2,4,6-tris(3,5-di-tert-butyl-4-~: hydroxybenzyl)benæene , ' ~ :

~3~

OH
t~Bu ~ , t^Bu CH3 ~ ~ aH3 t Bu ~ ~ CH2 ~1 CH2 ~ , t Bu HO ~ ~ C 3 1 ~ OH
t Bu t-Bu (In the above and subsequent formulae, t.Bu represents a tert-butyl group~
(c) 1,3,5-tris(4-tert-Butyl-3-hydroxy-2,6 dimethyl-benzyl ) is o cyanate toBU
~ OH

3 ~ CH3 0~ O

C~ CB2 OH OH

(d) tris( 3, ~Di-tert-butyl-4-h;Tdro3{;ybenzyl)iso-cyanurate ~:

: :

;

OH
t-Bu ~ , t~Bu O~ f o t.Bu ~ ~ CH2~ ~ `CH2 ~ , t~Bu HO ` OH
t-Bu t-Bu (e) n-Octadecyl 3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate t Bu HO ~ ~ CH2CH2COOc18 37 t^Bu (f) Nickel salt of a monoethylester of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid) ( B~CB2-P-O ) l~i (g) 2,2'-dihydroxy-3t3'-di(~-methylcyclohexy1)-5,5'-dimethyl-diphenylmethane H OB~

: CH3 CH3 ~3~3 _ 7 (h) 4,4=Thiobis(3-methyl-6-tert-butylphenol) ,CH3 ,t-Bu HO ~ S- ~ OH
t-Bu CH3 (i) 1,1,3-~ris(2-methyl-4-hydroxy-5-gert-butyl-phenyl)butane 3 ~ OH
CH3 l ll HO ~ CH -CH3-CH t-Bu t-Bu ~ CH3 ~ t.Bu aH3 OH

(j) ~etrakis~methylene 3-(3~5-di-tert-bu-tyl-4-hydro-xyphenyl)propionate~methane t Bu C (cH2ococ~I2cH2~oH
-t-Bu (k) 4,4'-Methylenebis(2,6-di-tert-butylphenol) t.Bu t.Bu HO~CE2~0H
t.B~ t.Bu The poly-l-butene polymer used in this inven-tion is preferably a homopolymer of l-butene, a copolymer of at least 90 mole % of l-butene and no-t more than 10 mole% of another a-olefin~ or a mixture of at least 50% by weight of the above homopolymer or copolymer with not more than 50/0 by weight of another a-olefin polymer. Examples of .

~3~3 ~-olefins other than l-butene are ethylene, propylene, 4-methyl-1-pentene, l-hexene and l-octene. The poly-l-butene polymer used in this invention especially preferably has a melt flow rate (to be abbreviated MER) of 0.1 to 50 g/10 minutes (measured in accordance with AST~ D-1238N). The poly-l-butene polymers used in this invention and methods for their manufacture are described, for example, in the specifications of United States Patents Nos.
3197452, 3219645, 3362940, 3244685, 3356666, 3907761 and 3865902.
The poly-l-butene resin composition of this invention may contain 100 parts by weight of the poly-l-butene polymer and usually 0.05 to 2.0 parts by weight, preferably 0.1 to 1.0 part by weight, of at least one hindered phenol selected from the group consisting of (a) to (k) above. If the content of the hindered phenol is lower than the above-specified lower lirni-t, the extent of improvement of the chlorine water resistance of the poly-l-butene resin composition tends to be considerably small.
A group of the hindered phenols (a) to (k) used in this invention give poly-l-butene resin compositions having improved chlorine water resistance and pressure-resistant strength.
Investigations of the present inventors have shown the above hindered phenols to be excellent in that the 3,5-di-tert-butyl-4-hydroxybenzoate (a) give the poly-l-butene resin composition of the invention which undergoes little degradation at its surface of contact with chlorine water when kept in contact with chlorine water, and the hindered phenols (b) to (k) give the poly-l-butene resin composition which has a relatively high degree of poly-merization and little decreases in its degree of polymerization when kept in contact with chlorine water~ In Examples given ~l .
,.~ ~ ' ~2~

hereinbelow, the degradation of the contacting surface is evaluated by measuring the gloss of the resin surface, and the degree of polymerization, by ':

' ' ., `~

:;``: ~ :
~, ~

- 8a -~2~ 3 measuring the solu-tion viscosity of the resin composition.
Preferably, the resin compo sition of this inven-tion contai.ns at least one 3~ 5-di~tert-butyl~4-hydroxy-benzoate (a) and at least one of the hindered phenols (b)

5 to (k).
The resin composition of this invention desirably contains at least one of co~pounds (1) to (n) shown below.
(1) 2,6-di-tert-butyl-p-cre~ol t-Bu H0 ~ CH3 t-Bu (m~ tris(2~4-di-tert-butyl-phenyl)phosphite t.Bu ( t~Bu ~ 0 ~ P

(n) tocopherol(a-, ~ or S-tocopherol, or a mixture of these) The resin Composition of this invention further containing at least one of the co~pounds (1) to ~n) is superior in that it has a higher degree Of polymerization than the resin Composition of this invention not containing -these compounds. ~he compounds (1) to (n) effectively prevent the poly-l~butene polymer from being degraded in the molten State by o~ygen and heat when it iS mixed with the hindered phenols (a) to (k). The resin composition of this invention which ~urther Contains at least one compound ~rom the group of (1) to (n) Contains at least one of (1) : to (n) in an amount of usually 0.01 to 1.0 part by weight~
preferably 0.05 to 0.5 part by weight~ per 100 parts by weight of the poly-l-butene polymer. When the content of the compound (1) to (n) is less than 0.01 part by weight~

_ 10 scarcely an~ effect is obtained of incorporating such a compound (1) to (n). I~, on the other hand, it exeeds 1.0 part by weight, -there is a tendency to the formation of a resin composition having a reduced tensile yield stress~
According to this invention, the resin composition further containing at least one of the compounds (1~ to (n) preferably comprises at least one of the 3,5-di--tert-butyl-4-hydroxybenzoates (a), at least one hindered phenol selected from the group consisting of the compounds (b) to (k) and at least one compound selected from the group of (1) to (n); or the compound (b~, the compound (e), the compound (j) and at least one compound selected from the group of (1) to (n).
~he aforesaid preferred resin compositions o~
this invention have improved chlorine wa-ter resistance both at the surface portion of a shaped articlea~d at the entire porting of a shaped article of resin, and exhibit reduced degradation of the polymer during molding~
Various known methods can be used to mix the poly-l-butene polymer with the compounds (a) to (n). For example, the individual ingredients are mixed by a ribbon blender or a Henschel mixer and then granulated by an extruder. Or they may be directly melted and mixed by a Banbury mixer, a kneader, a two-roll mill, etc. and then granulated by an extruder.
As required, other ultraviolet absorbers, mold-proof agents, rust inhibitors, lubricants, fillers, pig-ments, dyes, heat stabilizers, etc. may be incorporated in the poly-l-butene resin composition of this invention.
Rust ~ormation on me~ting and processing machines caused by the catalyst residue can be conveniently inhibited by using as the rust inhibitors a metal salt of a higher ~atty acid, or a double compound of the general formula M ~ly(oH)2x+3~-2z(A)z aH2 wherein M represents Mg, Ca or Zn, A respresents a divalent anion~ x, y and z are positive numbers, and a is 0 or a positive number~
Since the resin composition of this invention has excell~llt chlorine water resistance ancl pressure-resistant strength~ it can be conveniently used as a material for pipe systems adapted for supplying water having chlorine dissolved therein, ~or e~ample tap water, or no~-potable industrial water sterilized with chlorineO
A water supply pipe may be molded from the poly-l-butene resirl composition of this inven-tion b~, for example~
melting the pol~ butene pol~mer having incoxporated therein at least one compound selected fro~ (a) to (n) at a temperature of 150 to 300C in an extruder, extruding the molten mixture through a die, sizing the extrudate, cooling the extrudate with cooling water at a temperature of 5 to 50C, and cutting or winding up the cooled product through a take-up device. ~he ex-truder may generally be a single~screw metering t~pe extxuder. ~he die ma~, ~or example, be of a straight head type, a cross head type or an offset type~ ~he sizing ma~ be carried out by a sizing plate method, an outside mandrel method~ a sizing box method or an inside mandrel method. A pipe coupl-ing joint may be molded by using a combination of an ordinary inaection molding machine and Q mold or a com-bination of a blow molding machine and a mold, and a hot water storage tank ma~ be molded by using a combination of a blow molding machine and a moldO
~he poly-l-butene resin composition o~ this in~en-tion can be used widely in cold and hot water supply systemsbecause it has improved ~hlorine water resistance while retaining superior pressure-resistant strength, internal pressure creep durability at high temperatures) high and low temperature properties and abrasion resistance in-5 herent to the poly-l-butene polymer.
~he following examples illustrate the presen-t invention in greater detail.

Example 1 One hundred parts by weight of poly-l-butene (MFR
0.8 g/10 min.' ASTM D-1238N); manufactured by Mitsui Petrochemical Industries, Ltd.), 0.15 part by weight of calcium stearate, 0.05 part by weight of synthetic hydrotalcite (DHT-4A, a trademark) and 0.4 part by weight of each of the compounds shown in Table 1 were mixed in a Henschel mixer, melted and extruded at 230C and then granulated by an extruder having a screw diameter of 20 mm.
The resulting pellets were melted for 10 minutes by a hot press at 200C, and then pressed by a cold press at 30C for 3 minutes to form a press sheet having a thickness of 1 mm. Test pieces, 10 mm x 150 mm in size, were cut off from the press sheet. Each test piece was set on a holder, and dipped in a vessel in which chlorine containing water having an effective chlorine concentration of 100 ppm and a temperature of 90C was passed at a rate of 1 liter/hour. The gloss (angle of incident light 45) and [~]
(in decalin at 135C) of each test piece with the lapse of time were measured.
Immediately after molding, all test pieces had a gloss in the range of 90 to 95%. The results are summarized in Table 1.

,~;i `

Table 1 _ ___ _ Gloss (%) ~] (d~/g) ____ ._ _.____ __ __. ___ _. _ Run No. Compound In the In the Initial In the in- 4th 8th value 8th week corporated week week _ 1 (a)-l 85 76 3.2 1.7 2 (a)-2 80 70 3.1 1.5 3 (b) 35 6 4.2 3.2 4 (c) 30 5 4.5 3.6 (d) 25 6 3.8 2.9

6 (e) 29 6 4.1 3.0

7 (f) 76 8 4.6 3.6

8 (g) 23 5 4.6 3.5 g (h) 23 6 4.2 3.4 (i) 60 6 3.7 2.9 11 (j) 9 5 4.3 2.8 12 (k) 45 12 4.7 1.0 13 (1) 57 25 4.6 3.4 14 (m) 25 5 4.6 0.8 (n) _70 10 4.5 1.0 ~ _ ~ _ ~
In the table, compound (a)-l is 2,4-di-tert-butyl-phenyl 3,5-di-tert-butyl-4-hydroxybenzoate, and compound (a)-2 is n-hexadecyl-di-tert-butyl~4-hydroxybenzoate.
The compounds used in the above experiments were all commercially available compounds which are sold under the ~ollowing trademarks:
(a)-l: Tinuvin 120*
(a)-2: Cyasorb UV-2908*
(b): Irganox 1330*
(c)o Syanox 1790*
(d): Goodrite 3114*
(e): Irganox 1076*
(f): Irgastab 2002*
(g): Nonox WSP*
(h): Santonox R*

*Trade Mark (i): ~opanol CA
Irganox 1010 (k) Antioxidant 702 (1): BH~
(m): Irgaphos 168 (n): vitamin E
~8lY~ yL=I_~y_~e~
Example 1 was repeated except that each of the compounds indicated in ~able 2 was used instead of each of the compounds indicated in Table lo The results are shown in Table 2.
.

able 2 Compara- Compound G10BS (/0) 1 _ r~ ~ ~d~
tive in- In the In the Initial In the Example corporated 4th 8th value 8th week week week _ _ _ _ _ 1 Not added 7 5 1.9 0.4 2 P 6 5 2.8 0~6 3; q 8 c; 2~6 Oa 7 4 r 6 5 3.3 0~6 s 6 5 _ 3.7 1.6 p: 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole : q: bis(2,2,6,6~tetrame-thyl-4-piperidyl)sebacate . r: dis-tearyl thiodipropionate s: pentaerythritol tetra(~-laurylthiopropionate) Examples 2 to 4 Example 1 was repeated except that 0.2 part b-y weight of each of the compounds indicated in Table 3 was : used instead of 0.4 par.t by weight of each of the compounds : : indicated in Table 1. ~he results are shown in Table 3.
::

~o ' .

~ 3 Example CompoundGloss (ojo) _ rnl (dB/~) incorporated In the In tlie Initiai1 In the : 4th 8th value 8-th ___ _ ~ ~ r _ _ week week _ ~ week 2(a3-1 and (b) 90 81 4~0 3.o 3(a)-2 and (c) 90 80 4~2 3.1 I _ _ (b) ~nd (k).~ _ _ 4.6 ~ he compounds indicated in ~able 3 were commercial-ly available under the tradenames shown below rable 1, Examples 5 to 9 Example 1 was repeated except that 0~2 part by weight of each of the compounds indicated in ~able 4 was used instead o~ 0.4 part by weight o~ each of -the compounds indicated in Table 1. The results are shown in ~able 4.

~able 4 - - - Glosc ~ r~l (d _ _ Ex- Compound incorporated In the In the Initial In the ample 4th 8th value 8th week week week _. ~ .
: 5 (a)~l, (f) and (m) 90 9o 4O8 4~4 6 (a)-l, (b) and (k) 9o 90 4~7 4>3 7 (a)~l, (b) and (n3 9o 90 4.7 4.3 8 (a)-l, (b) and (m) 9o 9o 4.9 4~5

9 (a)-1, (b) and (1) 9o 90 _ _ 4.2 The compounds indicated in Table 4 were com-mercially available under the tradenames indicated below Table 1.
Example 10 Example 1 was repeated except that the four compounds indicated in ~able 5 were used in the indicated amounts instead o~ 0.4 part by weight o~ each of the ~L2 compounds shown in Table 1. The results are shown in Table 5~.

Tabl e 5 Compounds _ Glo s s (~_ --14/~) (parts by weight) In the In the Initial In the 4th week 8th week value 8th week ___ _ _ (b) (o. ~) (e) (0~ 3) 85 65 4~6 (i) (0.3) (1) (0.1) ._ _ ___ _ _.

~'

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A cold or hot water supplying pipe capable of supplying cold or hot water containing sterilizing chlorine dissolved therein, said pipe being composed of a resin composition comprising a poly-1-butene polymer and at least one hindered phenol selected from the group consisting of (a) 3,5-di-tert-butyl-4-hydroxybenzoates of the following formula wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms;
(b) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, (c) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, (d) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, (e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, (f) a nickel salt of a monoethyl ester of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid), (g) 2,2'-dihydroxy-3,3'-di(.alpha.-methylcyclohexyl)-5,5'-di-methyl-diphenylmethane, (h) 4,4'-thiobis(3-methyl-6-tert-butyl-phenol), (i) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)-butane, (j) tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate)methane, and (k) 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine.

2. The cold or hot water supplying pipe of claim 1 wherein the resin composition further comprises at least one compound selected from the group consisting of (l) 2,6-tert-butyl-p-cresol, (m) tris(2,4-di-tert-butyl-phenol)phosphite, and (n) tocopherol.

3. The cold or hot water supplying pipe of claim 2 wherein the resin composition comprises the poly-1-butene polymer and at least one of the 3,5-di-tert-butyl-4-hydroxybenzoates (a), at least one hindered phenol selected from the group consisting of the compounds (b) to (j) and at least one compound selected from the group consisting of the compounds (k) to (n).

4. The cold or hot water supplying pipe of claim 1 wherein the resin composition comprises the compounds (b), (e) and (j) and at least one compound selected from the group consisting of (l) 2,6-tert-butyl-p-cresol, (m) tris(2,4-di-tert-butyl-phenol)phosphite, and (n) tocopherol.

5. A method for providing a poly-1-butene resin composition with chlorine water-resistance and pressure-resistance for both cold and hot water having a minor amount of sterilizing chlorine dissolved therein, said method comprising incorporating in said poly-1-butene resin composition a stabilizing effective amount of at least one hindered phenol selected from the group consisting of (a) 3,5-di-tert-butyl-4-hydroxybenzoates of the following formula wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms;
(b) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene, (c) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, (d) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, (e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, (f) a nickel salt of a monoethyl ester of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid), (g) 2,2'-dihydroxy-3,3'-di(.alpha.-methylcyclohexyl)-5,5'-di-methyl-diphenylmethane, (h) 4,4'-thiobis(3-methyl-6-tert-butyl-phenol), (i) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane, (j) tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate)methane, and (k) 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine.

6. A method for supplying cold or hot water having a minor amount of sterilizing chlorine dissolved therein in a pipe composed of a poly-1-butene resin composition which pipe maintains its surface luster and exhibits only a small amount of decrease in the degree of polymerization of the poly-1-butene polymer when kept in contact with the chlorine-containing water for long periods of time, wherein a stabilizing effective amount of at least one hindered phenol selected from the group consisting of (a) 3,5-di-tert-butyl-4-hydroxybenzoates of the following formula wherein R represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms;
(b) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene, (c) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, (d) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, (e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, (f) a nickel salt of a monoethyl ester of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid), (g) 2,2'-dihydroxy-3,3'-di(.alpha.-methylcyclohexyl)-5,5'-di-methyl-diphenylmethane, (h) 4,4'-thiobis(3-methyl-6-tert-butyl-phenol), (i) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)-butane, (j) tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate)methane, and (k) 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) in an amount effective to provide said polymer with resistance to chemical degradation from the effects of said sterilizing chlorine is incorporated in the poly-1-butene polymer.

7. The cold or hot water supplying pipe of claim 3 wherein the poly-1-butene polymer is a homopolymer of 1-butene, a copolymer of at least 90 mole% of 1-butene and not more than 10 mole% of another alpha-olefin, or a mixture of at least 50% by weight of said homopolymer or copolymer with not more than 50% by weight of another alpha-olefin.

8. The cold or hot water supplying pipe of claim 3 which comprises 0.05 to 2.0 parts by weight of at least one additional said hindered phenol selected from the group consisting of (b) to (j) per 100 parts by weight of the poly-1-butene polymer.

9. The cold or hot water supplying pipe of claim 3 which comprises 0.01 to 1.0 part by weight of at least one compound selected from the group consisting of (k) to (n) per 100 parts by weight of the poly-1-butene polymer.

10. The cold or hot water supplying pipe of claim 3 which comprises 0.05 to 2.0 parts by weight of at least one said compound (a).

11. The cold or hot water supplying pipe of claim 3 which comprises, per 100 parts by weight of the poly-1-butene polymer 0.05 to 2.0 parts by weight of at least one said hindered phenol (a), 0.05 to 2.0 parts by weight of at least one additional said hindered phenol selected from the group consisting of the compounds (b) to (j), and 0.01 to 1.0 part by weight. of at least one said compound selected from the group consisting of (k) to (n).

12. The cold or hot water supplying pipe of claim 11 wherein the poly-1-butene polymer is a homopolymer of 1-butene, a copolymer of at least 90 mole% of 1-butene and not more than 10 mole% of another alpha-olefin, or a mixture of at least 50% by weight of said homopolymer or copolymer with not more than 50% by weight of another alpha-olefin.

13. A cold or hot water supplying pipe comprising a poly-1-butene polymer, (b) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, (e) n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, (j) tetrakis-(methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)-methane, and at least one compound selected from the group consisting of (l) 2,6-tert-butyl-p-cresol, (m) tris(2,4-di-tert-butyl-phenol)phosphite, and (n) tocopherol.

14. The cold or hot water supplying pipe of claim 13 wherein the poly-1-butene polymer is a homopolymer of 1-butene, a copolymer of at least 90 mole% of 1-butene and not more than 10 mole% of another alpha-olefin, or a mixture of at least 50% by weight of said homopolymer or copolymer with not more than 50% by weight of another alpha-olefin.

15. The cold or hot water supplying pipe of claim 13 which comprises, per 100 parts by weight of the poly-1-butene polymer, 0.05 to 2.0 parts by weight of each of the compound (b), the compound (e) and the compound (j) and 0.01 to 1.0 part by weight of at least one of said compounds (1) to (n).