JPS58500065A - Method for manufacturing polyolefin molded products - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for manufacturing polyolefin molded products Polyolefin tubes conducting water or aqueous media are subject to uncertain conditions under compressive stress at high temperatures. Shows durability. Different test water qualities and/or different test configurations depending on the composition of the medium. In Prufanfbau, the canal undergoes a chemical process from inside to outside very quickly. It was found that it can be decomposed into

The amorphous parts of the polyolefin structure undergo oxidative decomposition after a certain induction period. material The material first undergoes pitting, which spreads until the material is unusable. Poly Olefins are permeable to oxygen. In closed systems made of polyolefin materials, oxygen If consumed, the resulting oxygen deficit is replenished through the wall and thus this The oxygen deficit is replenished through the increasingly damaged polyolefin partition.

This material can be used in contact with aqueous media, such as in sanitary installations or underfloor heating, and in other When used in combination with metallic materials, especially non-metals, there are many possible negative effects. He can at least predict it.

As a result of the tests carried out, conformal of Cr, MnrFe”, co”, Cu”, and Zn2+ present Transition metal ions and oxo complexes of titanium and vanadium have a certain induction period. It was later discovered that this can cause extremely rapid material decomposition. At this time, the catalyst The decomposition reaction promoted by Depends on temperature and pressure. catalyzed by transition metal ions as an indicator. decomposition is highly stress dependent, and catalyzed decomposition is This is caused by a slight stress dependence of a fraction of a second.

The circumferential stress during the logarithmic useful life of static durability tests in wet conditions In the case of polybutene-(1), the dependence on 0.9+ for catalytically suppressed favorable aging in circumferential stress 0. I N-N-1a and 0.25 + for catalyzed aging 0. I N-1-.

The present invention eliminates such drawbacks of conventional polyolefin moldings and /or Polyolefin molding under pressure and contact with aqueous aggressive media Based on the problem of improving the long-term durability of objects.

Surprisingly, it has been shown that the synergistic action of stabilizers can eliminate the above-mentioned drawbacks. It became clear.

The method for manufacturing polyolefin molded products of the present invention includes adding the following i to a polyolefin melt. A11J:a) Copper (n) ion deactivator b) Sterically hindered phenolic antioxidants and sulfide synergists C) phosphite or organic phosphonite and d) Dialkyl disulfide and the additives are treated with a reactive resin that is chemically compatible with these additives. [1] and the polyolefin thus stabilized. It is characterized by processing the fin melt into a molded product.

Polypropylene copolymer, polypropylene (1) and crosslinked polyethylene, However, polybutene-(1) in particular has been found to be a particularly suitable polyolefin.

fA (It) As an ion deactivator, l,2-dicarboxylic acid dihydrazide, 1,2-dicarboxylic acid dihydrazone, substituted or unsubstituted benzoylhydrazide and benzoyl hydrazones or triazoles, preferably oxalyl-bi (benzylidene hydrazide), oxalyl hydrazide, m-nitrobenzhydrazide Preference is given to those selected from the group of radides or 1,2,4-) lyazoles.

A surprising synergistic effect was demonstrated using at least two of the various copper (It) ion deactivators. Occurs in some cases. Copper (It) ion deactivator: 0 per 100 parts of polyolefin ．． It is used in amounts of 1 to 0.8 parts, preferably 0.1 to 0.6 parts.

As an antioxidant, it has an 8,5-di-tert-butyl-4-hydroxyphenyl group. For example, tetrakis-[methylene-(3,5-di-tert-butyl-4-hydro) xyhydrocinnamate)]-methane is particularly suitable. Also, screws (2, 2’ -methylene-bis(Φ-methyl-6-tert-butylphenol) terephthalate] and 1+3+5-)lis(3,5-di-tert-butyl-4-hydroxy Benzyl) isocinnamate is also a suitable antioxidant. The amount used is polyolefin The amount is 0.1 to 0.7 parts, preferably 0.4 parts per 100 parts of the water.

Examples of sulfide synergists for antioxidants include dialkyl sulfides, e.g. Dilauryl-thiodipropionate has been found to be suitable. The amount used is polio The amount is 0.1A-0.7 parts, preferably 0.4 parts per 100 parts of refin.

sub! J> Entire series of acid esters, e.g. distearyl phosphite, tris Thearylphosphite, pentaerythrityl phosphite (preferably acetovine vinegar) Acid Diventaerythritol Phosphite Ester Matahei Sophthalic Acid Dipentaerythritol trit phosphite ester), pentaerythrityl phosphite (preferably (distearylpentaerythrityl diphosphite), sugar alcohol phosphite (preferably distearyl-β-hydroxytriacontyl-sorbityltritri) Phosphites) or triarylphosphites are suitable for the process of the invention.

Phosphite esters having a melting point of 80-120°C, optimally 100°C. It is preferable to select Also, organic phosphonite is used instead of phosphite. I can be there. The action of the sulfide synergist has a molecular weight of 200 to 8000, preferably 400-4o00 wax, 5-75 parts per 100 parts of phosphite It is enhanced by adding in the amount of .

The overall phosphate ester concentration is 0.01 to 0.15 parts per 100 parts of polyolefin. , preferably between 0.2 and 0.8 parts.

The process according to the invention includes the entire series of dialkyl disulfides, in particular the formula (5-CH-CH- 000-C□8H87)2 2 in an amount of 0.1 to 0.7 parts, preferably 0.4 parts per 100 parts of polyolefin. It can be used in amounts.

Add the above additives to a polymer alloy or polymer of reactive resin and polyolefin. Polymer matrices in the form of polymer-assoziate A chemically compatible reactive resin suitable for the polyolefin melt is used for fixation to the polyolefin melt. A resin, preferably an epoxide resin, is added.

Bisphenol-bichlorohydride with epoxide equivalent weight of 500-1000 064 to 1.0 parts i of phosphorus epoxide resin per 100 parts of polyolefin It is particularly suitable to add 1 liter.

The action of the reactive resin is during melt molding (be im schmetzr-ormen of polymers caused by reactive groups and/or processing techniques from stabilizers in via a possible chemical reaction with a reactive group from the change and/or in combination (A zzociate) and/or through morphological effects.

To further improve the long-term durability of polyolefin molded products produced according to the present invention When processing a polyolefin melt into a molded article, the side of the material facing the aqueous medium must be The tissue can be densified.

Another measure of the invention is a selected stress state in the molding. melt molded When the material interface faces the aqueous medium to which a compressive force has previously been applied and the tensile force has previously applied Try to make the interface opposite to the aqueous medium being added. For this, the opposite Changes are necessary in terms of cooling.

The solution to the above problem is expressed as the logarithm per unit compressive stress change at 95°C. Effective life ranges from 0°25±0.1 unit/stress unit to 0.9±0.1 unit/stress unit When extended to material properties are significantly improved.

The advantages achieved by the present invention include the selection and use of novel synergistic additives. By immobilizing the additive in a polymer matrix, it is possible to M-transfer metal iono-Fe, cu”, zn”, etc. present in the polymer matrix The additives combined in the TRIX allow the catalyst to remain ineffective within the amorphous region. complexed with a chelate, and the immobilization of said additives is additionally applied to the moldings at the surface. can be optimized in terms of organization depending on how it is used, which allows the invention to In that the long-term durability of the produced polyolefin moldings is decisively improved. Essentially acceptable.

It is obvious that the invention can be modified in a wide variety of ways, and the following examples are merely intended to illustrate the invention. Merely illustrating the invention0 Example 1 100 parts of extremely slightly pre-stabilized polybutene (1) particles were heated with nitrogen in a kneader. ・165 parts at 5°C under an inert gas atmosphere Pentaerythryl-tetrakis (3-(3,5-di-tert-butyl-*-hydroxy) -phenyl]-propionate 2f (ILtlJβ, β'-thiodipropionate Acid dilauryl ester 2 parts by weight β,β'-distearyl dithiodipropionate Ester 2 parts by weight Trialkylphosphite (melting point 100°C) 1.5fi ti1M.

Oxalyl dihydrazide 2.4-tllJ oxalyl bis(benzoyl dihydride radide) 2.4 fl (@I bisphenol-A-epichlorohydrin epoxy af fat 5-fold i11 calcium stearate i, a melted into a concentrate with a superposition s , mixed and extruded into Φ granules.

・When passing 1 part by weight of the obtained concentrate through the second kneader, 9 parts of polybutene (1) was added. Diluted by volume.

These particles were then further processed into 16×2 tubes, for example by an extruder. melt Heat is removed after melt molding. By sprinkling water in a nozzle device\ The inside of the tube was cooled for \0.5-0.8 seconds. The sensible heat and heat of vaporization of the sprayed water are The heat capacity is 5 to io times that of cooling a melt formed into a tube below the freezing point of the tube. It had a quantity.

Move it 10cm or delay it for 1.5-3 seconds to create a ring-shaped shower and Vaku umaussenka-1ibrierung) Added external cooling using

Although the bursting strength of the tube decreased due to supercooling, it was effective when the circumferential stress was low. It's been long. It was possible to narrow the scattering range regarding the useful life.

In response to the resulting phase change, the inner tube has a significantly higher density than the outer tube, i.e. 0 ．． A 4% higher density was measured in the amorphous region. In the durability test, the tube was made of Fe(■), C remains flexible many times longer even in the presence of u(■) and Zn(I[) ions. and did not suffer from brittle fracture.

At 125°C, the moldings (1 g) produced according to the invention are containing 1 g of copper (It), 19 g of Zn (If) or 1 g of Fe ([1)] In a metal ion aqueous solution 10 - I) H1 with 501 nl of oxygen from air and 1 after 1000 hours in contact compared to commercially available polybutene-(1) It showed a significantly reduced oxygen consumption jl (pressure drop) of 4%.

The durability of the 16x2mm tube extruded from the material made according to the invention is When a non-ferrous metal is screwed on the outer surface of the 0.65 logarithm per unit circumferential stress difference tested between bar) and 19 bar Extended useful life of unit very slightly pre-stabilized polybutene-(1) grains 100 parts of the powder was heated in a calender (145-165° C), mixed and 200 parts rolled into shapes at 10°C.

Example 3 100 parts of extremely slightly pre-stabilized polybutene (1) particles were added in a kneader to It was melted into a concentrate with additives, mixed and continuously granulated.

Calcium stearate 2 parts by weight Antioxidant 2 parts by weight Epoxy resin 10 parts by weight β,β′-thiodipropionic acid dilauryl ester 2 heavy 111β,β′-di Thiodipropionic acid stearyl ester 2 parts by weight oxalyl bis(benzoic acid) hydrazide) 1 part by weight trialkyl phosphite 1.5 m11M point After diluting 10 times with Livten-(1), it was treated in the same manner as in Example 1. present invention Water brought into contact with tubes made by extruding materials produced by The tube showed significantly improved durability compared to conventional tubes.

Example 4 100 parts of extremely slightly pre-stabilized polybutene (1) particles were added in a kneader to It was melted into a concentrate with additives, mixed and continuously granulated.

Calcium stearate double @ part Antioxidant 1 weight Epoxy resin 1 part by weight β, β'-thiodipropionic acid dilauryl ester 2 111 parts β, β'-dilauryl ester Thiodipropionic acid stearyl ester 2 parts by weight oxalyl bis(benzoic acid) hydrazide) I 11 parts bis2,2'-methylene-bis-(4-methyl -6-tert-butylphenol) tetraphthale) 1 heavy ill organic phosphite G 1.5 weight 1 part After diluting 10 times with polybutene (1), it was treated in the same manner as in Example 1. present invention Tubes made by extruding the material produced by It showed significantly improved durability compared to conventional tubes.

Submission of Translation of Written Amendment (Patent Law Section 184 Section 7, Paragraph 1) August 28, 1982 Mr. Kazuo Wakasugi, Commissioner of the Patent Office l Display of patent application POT/CHs110oos12 Name of invention Polyolefin Method for manufacturing molded products 3, patent applicant Address: Zäher-8201 Schaffhausen Muer Rentalstra, Switzerland Se105 Name Georg Fischer Akchengesellschaft Representative Link Fau El The same Luzalday V.G. Nationality: Switzerland 4. Deputy manager Location: 7th floor, Kayama Building, 3-2-4 Kasumigaseki, Chiyoda-ku, Tokyo, 1 (A) Phone +58112241 (representative) Name (5925) Patent attorney Hide Sugimura Akatsuki 1 other person 5. Date of submission of written amendment December 2, 1981 6. List of attached documents (1) One translation of the written amendment Amended scope of claims (Received at the International Bureau on December 2, 1981 (02, 12, 81)) Box 1 to 81 (Delete) 32 Especially in polyolefin molded articles having a polybutene-(1) matrix. hand, The polyolefin molded article contains a transition metal ion deactivator, and the polyolefin molded article contains a transition metal ion deactivator. The activator is chemically bonded to the above-mentioned IJ socks via the oligomeric reactive resin. Polyolefins characterized by being fused or polymerically inlaid. Fin moldings.

33 Fe- with transition metal ion deactivators of various valences.

Claim characterized in that it is effective against Cu- and Mn- ions. Fin molding.

34 The M transfer metal ion deactivator is a carboxylic acid hydrazide or a 1,2-radical Claims 1 or 2 belong to the group of bolic acid dihydrazides. is the polyolefin molded article according to item 2.

35, 1.2-Dicarboxylic acid dihydrazide is oxalyl dihydrazide The polyolefin molded article according to item 3 in the range of .

364 0.1 to 0.364 transition metal ion deactivator per 100 parts of polyolefin. 8 parts, preferably 0.1 to 0.6 parts. The polyolefin molded article according to any one of items 1 to 4 of the range.

37 Phenolic antioxidant whose polyolefin molding is sterically hindered and a sulfide synergist. The polyolefin molded article according to any one of the items.

38, the antioxidant has a 3,5-ditert-butyl-4-hydroxy-phenyl functional group. The polyolefin molded article according to claim 6, characterized in that it has a polyolefin molded article.

39 The following compounds are antioxidants: a) Tetrakis-[methylene-(3,5-di-tert-butyl-Φ-hydroxyhydride rosinnamate) monomethane b) 1,3.5-)lis(3,5-ditert-butyl-4-hydroxybenzyl)i Socinnamate C) Bis[2,2'-methylene-bis(4-methyl-6-tert. Contains one or more of the following: The polyolefin molded article according to claim 6, characterized in that:

40 antioxidant per 100 parts of polyolefin, preferably 0.1 to 0.7 parts, preferably Claims 7 or 8, characterized in that 0.4 parts are used. Polyolefin molded product.

41.Specifically, the polyolefin molded product contains dialkyl disulfide. The polyolefin composition according to any one of claims 1 to 9, characterized in that figure.

The dialkyl disulfide has the formula (s-an-OH-coo-c, 8c87 )22 The poliovirus according to claim 1O, characterized in that Refin moldings.

43 Dialkyl disulfide content is 0.1 to 100 parts of polyolefin 11 of the claims characterized in that it is 0.7 part, preferably 0.4 part. The polyolefin molded article described.

44 Claims 1 to 1, wherein the reactive resin is an epoxy resin The polyolefin molded article according to any one of Item 2.

45 Epoxy resin to bisphenol - epichlorohydrin - epoxy resin 14. The polyolefin molded article according to claim 13, characterized in that:

46 The epoxy resin has an epoxide equivalent weight of 500 to 1000 The polyolefin molded article according to claim 13 or 14.

47. 0.4 to 1.0 parts of reactive resin per 100 parts of polyolefin, preferably Claims 13 to 15, characterized in that: 2) is used in an amount of 0.6 parts; The polyolefin molded article described in any one item.

48 Polyolefin molding according to any one of claims 1 to 6 How things are manufactured.

49 Transition metal deactivator during polyolefin compounding and/or melt extrusion The method according to claim 17, characterized in that the method is made to react with a reactive resin Law.

50M, characterized in that the transfer metal ion deactivator is oxalyl dihydrazide 18. The method according to claim 17.

51 Material side facing the aqueous medium when processing the polyolefin melt into a molded product Claims 17 to 19, characterized in that the structure maintains the denseness of the structure. A method described in one of the sections.

52. When melt-molding a polyolefin melt, at the material interface facing the aqueous medium, The feature is that compressive force is applied in advance and tensile force is applied in advance to the side opposite to the aqueous medium. 21. A method according to any one of claims 17 to 20.

53 During melt molding, the material surface facing the aqueous medium is strongly cooled and the surface opposite to the aqueous medium is cooled. 22. A method according to claim 21, characterized in that the opposing surfaces are cooled with a delay.

54. Melt forming consists of extruding a tube with reverse cooling, and this deboning is done internally by water sprinkling. Claims characterized in that cooling and external cooling with a time delay downstream The method according to paragraph 22 of the box.

55 The density of the structure is determined by the material side facing the aqueous medium facing the opposite side of the aqueous medium. Claims characterized in that the amorphous region is 0.4±0.1% higher than the surface. 29. A method according to any one of paragraphs 17-28 of the range.

56 Polyolefin composition according to any one of claims 1 to 16 Use of shapes for transporting or storing aqueous media.

57. Method of use according to claim 25 at high temperature and/or high pressure .

58. The method according to claim 25, wherein the aqueous medium is drinking water. how to use.

international search report Continuation of page 1 9-shot clearer Strerel Billy Zeher, Switzerland - 8200 Schaffhause Germany - 7700 Schaffhause Ngen Huolbelstrasse 4

Claims (1)

[Claims] 1. When producing polyolefin molded products, the following additives are added to the polyolefin melt: Additive: a) Copper (It) ion deactivator b) Sterically hindered phenolic antioxidants and sulfide synergists C) M phosphate ester or organic phosphonite and d) Dialkyl disulfide and the additives are treated with a reactive resin that is chemically compatible with these additives. (polymer matrix) IJ Lux is fixed, and the above-mentioned polio stabilized in this way is A polyolefin molded article characterized by processing a refin melt into a molded article. How it's made. 2 Polypropylene copolymer, polypropylene-(1) or polyolefin The method according to claim 1, characterized in that cross-linked polyethylene is used. . 3 A claim characterized in that polybutene-(1) is used as the polyolefin The method described in Scope No. 1. 4. Copper (I[) ion deactivator is 1,2-dicarboxylic acid dihydrazide, 1, 2-dicarboxylic acid dihydrazone, substituted or unsubstituted benzoyl hydrazide or and benzoylhydrazones or triazoles. A method according to any one of claims 1 to 3. 5 Copper (It) ion deactivator is the following compound: a) Oxalyl-bis(benzi Lyden hydrazide) b) Oxalyl dihydrazide C) m-nitrobenzhydrazide d) l,2.4-h lyazole 5. The method according to claim 4, wherein the method is one of the following. 6. The copper (U) ion deactivator is a compound according to claim 4 or 5. It is characterized by being composed of compounds having synergistic effects of at least two of the following: The method according to claim 4 or 5, characterized in that: 7 Copper (n-) ion deactivator in an amount of 0.1 to 0.8 per 100 parts of polyolefin. part, preferably from 0.1 to 0.6 parts. The method according to any one of items 4 to 6. 8. The antioxidant has a 8,5-ditert-butyl-4-hydroxy-phenyl functional group. The method according to any one of claims 1 to 7, characterized in that . 9 Compounds in which the antioxidant is the following: a) Tetrakis-[methylene-(3,5-di-tert-butyl-4-hydroxy- drocinnamate)]-methane b) 1,8,5-tris(3,5-cytert-butyl -4-hydroxybenzyl)isocinnamate C) Bis[2,2'-methylene -bis(4-methyl-6-tert-butylphenol) terephthalate] Any one of claims 1 to 7, characterized in that it is a species or two or more species. The method described in section. 0.1 to 0.7 parts of IO antioxidant per 100 parts of polyolefin, preferably 10. A method according to claim 8 or 9, characterized in that 0.4 part is used. 11. Claims characterized in that the sulfide synergist is dialkyl disulfide A method according to any one of ranges 1 to 10. 12. Claim that the dialkyl sulfide is dilauryl-thio-dipropionate The method according to item 11. 13 0.1 to 0.7 parts of sulfide synergist per 100 parts of polyolefin, preferably or in an amount of 0.4 parts. The method described in Section 2. 14. Phosphite ester is distearyl phosphite, tristearyl phosphite dipentaerythrityl phosphite (preferably dipentaerythrite acetoacetate) Erythritol phosphite or isophthalic acid pentaerythrityl phosphite (preferably distearyl ester), pentaerythrityl phosphite (preferably distearyl ester), erythrityl diphosphite), sugar alcohol phosphite (preferably diphosphite), Stearyl-β-hydroxytriacontylusolpityltriphosphite) Claims 1 to 13 characterized in that the compound is triarylphosphite or triarylphosphite. The method described in any one of the following sections. 15 In addition to phosphite ester, molecular Ji400-4000 (7) wax preferably in an amount of 5 to 75 parts per 100 parts km of phosphite ester. 15. A method according to claim 14, characterized in that: 16 Phosphite has a melting point of 80 to 120°C, preferably 100°C. 16. The method according to claim 14 or 15, characterized in that: 17 Kanatsuri phosphate ester concentration is 0.0% per 100 parts of polyolefin. O1~0. Claims 14 to 16 characterized in that the amount is 3 parts, preferably 0.15 parts. The method described in any one of the following sections. 18, Schiff #ki/l/disulfide has the formula (S-CH2-CH2-C00- Claims 1 to 17 characterized by being represented by C□8C1)2 The method described in any one of the sections. 19 0.1 to 0.7 dialkyl disulfide per 100 parts of polyolefin according to claim 18, characterized in that it is used in an amount of 0.4 parts, preferably 0.4 parts. Method described. 20 Claim 1-19 characterized in that the reactive resin is an epoxy resin The method described in any one of the sections. 21 The epoxy resin is bisphenol A-epichlorohydrin-epoxy resin. 21. A method according to claim 20, characterized in that: 22, characterized in that the epoxy resin has an epoxide equivalent weight of 500 to 1000 21. The method according to claim 19 or 20. 23. 064 to 1.0 parts of reactive resin per 100 parts of polyolefin, preferably Any one of claims 20 to 22, characterized in that is used in an amount of 0.6 parts. or the method described in one of the sections. 24 Material side facing the aqueous medium when processing the polyolefin melt into a molded product Claims 1 to 23, characterized in that the structure maintains a dense structure. method described in one of the following sections. 25 When melt-molding a polyolefin melt, at the material interface facing the aqueous medium, The feature is that compressive force is applied in advance and tensile force is applied in advance to the side opposite to the aqueous medium. 25. A method according to any one of claims 1 to 24. 26 During melt molding, the material surface facing the aqueous medium is strongly cooled and the surface opposite to the aqueous medium is cooled. 26. A method according to claim 25, characterized in that the opposing surfaces are cooled with a delay. 27 Melt forming consists of extruding a tube with reverse cooling, and this deboning is done inside by water spraying. Claims characterized in that cooling and external cooling with a time delay downstream The method according to paragraph 26. 28 The density of the structure is determined by measuring the density of the structure by determining the density of the structure on the material side facing the aqueous medium and Claims characterized in that the amorphous region is 0.4±0.1% higher than that in the amorphous region. 27. The method according to any one of paragraphs 24 to 27. 29 Any one of claims 1 to 28 G manufactured by the method described in this molded polyolefin. 30, the polyolefin molded article according to claim 29 is transported in an aqueous medium or or storage usage. 31. Method of use according to claim 30 at high temperature and/or high pressure .