CA2239507A1 - Process for producing flame-retardant, silane-crosslinked polyolefin - Google Patents
Process for producing flame-retardant, silane-crosslinked polyolefin Download PDFInfo
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Abstract
A process for producing a flame-retardant, silane-crosslinked polyolefin, characterized by melt-mixing a flame-retardant polyolefin consisting of an .alpha.-olefin polymer, a flame-retardant, a water-absorbing agent and a silanol-condensing catalyst with a substantially water-free carrier polymer comprising an organic unsaturated silane and a free-radical generator at a higher temperature than the crystalline melting point of the base polymer of the flame-retardant polyolefin to subject them to reaction and then contacting the reaction mixture with water to subject the reaction mixture to crosslinking.
Description
CA 02239~07 1998-06-04 W O97/24401 PCT/JP9~ 3/~4 DESCRIPTION
~ PROCESS FOR PRODUCING FLAME-RETARDANT, SILANE-CROSSLINKED POLYOLEFIN
TECHNICAL FIELD
This invention relates to a silane-crosslinking process for producing a flame-retardant, silane-crosslinked polyolefin in one step using a carrier polymer cont~; n; ng an organic unsaturated silane or the like at a high concentration in the silane-crosslinking of a flame-retardant polyolefin cont~; ni ng a silanol-co~nsing catalyst and a flame-retardant.
BACKGROUND ART
In order to impart a flame-retardancy to a polyolefin composition which has been often used in coat-ing wires, cables and the like; hoses; sheets; injectionmoldings; and the like, a halogen compound and diantimony trioxide have heretofore been added to the polyolefin to achieve the flame-retardancy. However, these composi-tions are halogen-containing compositions, so that halo-gen gases, which are not only harmful in themselves butalso the cause of metal corrosion, are generated when they are burned. Therefore, these compositions have not been desired. In addition, the amount of smoke yenerated is large, the visibility b~r~ -~ bad and the people have been markedly prevented from taking refuge from a fire CA 02239~07 l998-06-04 W O 97/24401 PCT/J ~ /s4 and from fighting a fire.
In particular, from a safety aspect, it has recentl~ been strongly required that such a halogen-con-taining gas be not generated. Under such circumstances, attention has been paid to an inorganic flame-retardant using a hydrated metal compound which generates very little fumes and is very little harmful.
In recent years, a resin composite cont~ n; ng magnesium hydroxide, aluminum hydroxide or the like has been put to practical use for imparting flame-retardancy;
however, these flame-retardant resin compositions can prevent the generation of halogen-cont~i n; ng gases but have a problem in that there is caused a so-called drip ph~nom~on that the resin compositions melt and drip dur-ing the firing or in that the resin compositions areinferior in shape-ret~;n~hility at high temperatures.
In order to improve the flame-retardancy and also the heat resistance to solve the above problem, there is a method of crosslinking the resin, and this is disclosed in, for example, JP-B-57-24373, JP-B-57-26620 and the like. ~owever, the method described therein requires a large scale crosslinking apparatus for chemi-cal crosslinking, crosslinking with electron beams or the like and hence the cost of the equipment per se and the expenses for subsequent operation, mainten~nce, control and the like of the apparatus are increased, resulting in an increase of the cost of the composition. Furthermore, as stated in JP-A-60-101129 and JP-A-60-147463, in the CA 02239~07 1998-06-04 case of a flame-retardant, crosslinked composition char-acterized in that a flame-retardant is added to a silane-grafted polyolefin resin and this silane-grafted poly-ole~in resin is finally crosslinked, only the silane-grafted polyolefin resin whose crosslinking has beencontrolled has been able to be used for preventing prema-ture crosslinking in bl~A; ng and kneading the flame-retardant with the silane-grafted polyolefin resin. As a result, it has been impossible to increase the degree of crosslinking of the silane-grafted polyole~in resin and hence the heat resistance has been insufficient.
The above method requires at least two reac-tion steps, namely, the silane-grafting reaction step and the silanol-condensing reaction step. Accordingly, at least two extrusion steps must be carried out and an economical difficulty of the final product is unavoid-able.
Furthermore, the Monosil TM process method is known as a one-step process. However, this method re-quires a liquid-~AA;~g means for injecting an organic unsaturated silane in the form of a liquid into an extruder and has problems of slippage and metering fail-ure. The extruder is also required to have a large L/D
and be of an expensive and special type for uniformly dispersing a small amount of an additive, and hence, an economical problem is unavoidable. In addition, a very sophisticated technique is necessary for the extrusion and hence there have been no comm~cialized method for CA 02239~07 l998-06-04 flame-retardant type.
In addition, JP-A-3-167229 discloses, as a one-step process, a silane-crosslinking method in which a silane has been introduced into a solid carrier polymer.
However, this method uses a porous polymer or EVA as the solid carrier polymer, and in this method, in addition to the silane and the free-radical generator, an additive such as a silanol-condensing catalyst, an antioxidant or the like is also introduced into the solid carrier poly-1~ mer. Therefore, an oligomer is formed by condensation ofthe silane or the crosslinking is inhibited by trapping the radical, whereby such problems are caused that cross-linking efficiency and storability are inferior. In said Japanese publication, no flame-retardant type is men-tioned.
This invention has solved these problems andaims at providing a silane-crosslinking method comprising silane-crosslinking a flame-retardant polyolefin contain-ing a silanol-condensing catalyst and a flame-retardant, wherein a flame-retardant, silane-crosslinked polyolefin is produced in one step using a carrier polymer contain-ing an organic unsaturated silane or the like at a high concentration.
~ISCLOSURE OF T~E INVENTION
This invention is a process for producing a f~ame-retardant, silane-crosslinked polyolefin which comprises melt-mixi ng (l) a flame-retardant polyolefin CA 02239~07 1998-06-04 comprising 100 parts by weight of an a-olefin homopolymer or copolymer having a density of not more than 0.92 ~ g/cm3, 50 to 200 parts by weight of a flame-retardant, 0.5 to 10 parts by weight of a water-absorbing agent and a catalytic amount of a silanol-condensing catalyst with (2) a su~stantially water-free carrier polymer comprising a free-radical generator and an organic unsaturated silane represented by the general formula RR'SiYz in which R is a monovalent olefinically unsaturated hydro-carbon group; Y is a hydrolyzable organic group; and R'is a monovalent hydrocarbon group other than the olefinically unsaturated hydrocarbon group or the same as Y, at a higher temperature than the crystalline melting point of the base polymer of the flame-retardant polyolefin to subject them to reaction; subse~uently, contacting the reaction mixture with water to subject the reaction mixture to crosslinking. Preferably, this invention provides the above process for producing a flame-retardant, silane-crosslinked polyolefin, charac-terized in that the a-olefin homopolymer or copolymer is a homopolymer of an a-olefin such as ethylene, propylene or the like, or a crystalline, block or random copolymer of an a-olefin with at least one other a-olefins, or a copolymer of a major amount of an a-ole~in with a minor amount o~ at least one polar monomer selected from vinyl acetate, maleic anhydride, acrylic acid and the like or a mixture of them and has a density of not more than 0.92 g/cm3; the carrier polymer is a polymer selected from the CA 02239~07 1998-06-04 group consisting of an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl methacrylate copolymer (EMMA), a hydrogenated block copolymer obt~ine.~ by hydrogenating a block copolymer consisting of at least one polymer block comprising mainly a vinyl aromatic compound and at least one polymer block comprising mainly a conjugated diene compound and a mixture of them; the amount of the carrier polymer added is 1 to 5% by weight; the flame-retardant is a magnesium hydroxide or all~m;nllm hydroxide surface~treated with at least one silane-coupling agent, a silicone derivative, a fatty acid or a metal salt of a fatty acid; and the water-absorbing agent is quicklime having an average particle size of 1 to 5 ,um surface-treated with at least one silane-coupling agent, a sili-cone derivative, a fatty acid or a metal salt of a fattyacid.
This invention is explained below in detail.
The a-olefin homopolymer or copolymer used in this invention is a homopolymer of an a-olefin such as ethylene, propylene or the like; a crystalline, block or random copolymer of an a-olefin with at least one other a-olefin, for example, a crystalline propylene-ethylene block copolymer, an ethylene-butene-l random copolymer or a propylene-butene-1 random copolymer; a copolymer of a major amount of an a-olefin with a minor amount of at least one polar m~nom~ such as vinyl acetate, maleic anhydride, acrylic acid or the like (including graft copolymers); or a mixture thereof, and has a density of CA 02239~07 1998-06-04 not more than 0.92 g/cm3. When the density exceeds 0.92 g/cm3, the compatlbility of the flame-retardant with the a-olefin homopolymer or copolymer becomes inferior and the flame-retardancy b~comes low.
The flame-retardant used in this invention is a compound-having a decomposition-starting temperature in the range o~ from 150~C to 450~C and represented by the general formula MmOn-XHzO in which M is a metal, m and n are integers of l or more determined by the valency of the metal M and X is a numeral showing the crystal water content, or a double salt cont~ n ~ ng said compound Spe-cific examples of said compound include alllm;n~lm hydrox-ide (Al203-3HzO or Al(OH)3), magnesium hydroxide (MgO-HzO
or Mg(OH)z), calcium hydroxide (CaO-HzO or Ca(OH)2), bari-um hydroxide (BaO-HzO or BaO-9HzO), zirconium oxide hy-drate ~ZrO-nH20), tin oxide hydrate (SnO-H20), basic magnesium carbonate (3MgCO3-Mg(OH)z-3HzO), hydrotalcite (6MgO-A1203.HzO), dawsonite (NazCO3-Al203-nHzO) and borax (Na20-B20s.5H20), and also include zinc borate, zinc meta-borate, barium metaborate, zinc carbonate, calcium magne-sium carbonate, calcium carbonate, barium carbonate, molybdenum oxide, red phosphorus, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, ethyl diethylenephos-phate, butyl dihydroxypropylenephosphate, disodium ethyl-~ ~n~phnsphate, ~mo~; um polyphosphate, melamine phosphate, guanidine phosphate and the like. These may be used alone or in combination of two or more, and magnesium CA 02239~07 l998-06-04 hydroxide and aluminum hydroxide are preferred.
The flame-retardant is preferably one surface-treated with (i) a silane coupling agent, (ii) a silicone derivative, (iii) a fatty acid, (iv) a metal salt of a fatty acid, or the like.
The silane-coupling agent.(i) is one having, at one end of the molecule, a reactive group (methoxy group, ethoxy group, carboxyl group, cellosolve group or the like) which reacts with an inorganic material, and generally, this has a trifunctional group in many cases;
however, those having a difunctional or monofunctional group as the above reactive group may also be used. At the other end, said silane-coupling agent has a reactive group (vinyl group, epoxy group, methacryl group, amino ~ 15 group, mercapto group or the like) which chemically bonds to the resin side which is an organic material, and the skeleton of the main chain thereof is an alkoxyoligomer.
The silicone derivative (ii) is of such a type that a part of the methyl group of dimethylpolysiloxane 2~ has been replaced by various organic groups, and the various modifying organic groups include a wide variety of modifying group derivatives, for example, modifying groups for the purpose of i~ ~vlng compatibility, hydro-philic property, lubricity, water-repellency and the like such as a-methylstyrene group, ~-olefin group, polyether group, alcohol group, fluoroalkyl group and the like;
modifying groups for the purpose of il..~lovlng the reac-tivity and moisture-absorptivity such as amino group, CA 02239~07 1998-06-04 mercapto group, epoxy group, carboxyl group and the like;
modifying groups for the purpose of releasing and luster-- ing which has been substituted by a higher fatty acid, carnauba wax and an amide; and the like.
The fatty acid (iii) includes saturated and unsaturated fatty acids having 6 to 22 carbon atoms, and specifically, stearic acid and oleic acid which have 18 carbon atoms are mentioned.
The metal salt (iv) of a fatty acid includes metal soap in which the above-mentioned fatty acids are bonded to metals, and specifically, sodium stearate, potassium stearate, sodium oleate, potassium oleate and the like are mentioned. Of course, the fatty acid may be of linear chain saturated type or unsaturated type, and those in which the side chain portion is bonded to the metal are, of course, effective.
When the flame-retardant surface-treated with one of (i) to (iv) or a mixture thereof is blended in an amount of 50 parts by weight to 200 parts by weight, it is compatible with or reacts with a low crystallinity polymer having a low density, and even when a large amount thereof is blended, it is possible to easily form a composition excellent in low-temperature characteris-tics, flexibility and processability. However, when the amount is less than 50 parts by weight, the flame-retard-ing effect thereof is remarkably lowered. When the amount exceeds 200 parts by weight, the fIame-retardancy is remarkably increased, but the mechanical characteris-- CA 02239~07 1998-06-04 W O 97f24401 PCT/J~9~ 4 tics including flexibility, low-temperature characteris-tics and the like are deteriorated and the processability becomes extremely bad.
The water-absorbing agent used in this inven-tion is ~uicklime (calcium oxide), magnesium oxide, bari-_ um oxide, all~m;n~lm oxide, magnesium-al~m;nl-m-oxide, m~n~ ~ium~all lm; ~llm ~ hydroxide-carbonate, silica gel, calcium sulfate anhydride or copper sulfate anhydride.
~uicklime is preferred, and those surface-treated with the above (i) to (iv) components or a mixture thereof are more preferable. This water-absorbing agent is added to reduce the amount of water att~che~ to the flame-retar-dant polyolefin. This is because when water is attached to the flame-retardant polyolefin, premature crosslinking is caused in the silane-crosslinking step. The amount of water causing this premature crosslinking is about 100 ppm or more, and in order to control the amount of water attached to less than 100 ppm, the water-absorbing agent must be added in an amount of 0.5 to 10 parts by weight.
When the amount is less than 0 5 part by weight, the amount of water attached b~co~ 100 ppm or more and premature crosslinking is caused. Even if quicklime is used in an amount of more than 10 parts by weight, the effect of reducing the amount of water attached is not increased and rather deterioration of mechanical charac-teristics is caused in some cases. In order to make the dispersibility in the flame-retardant polyolefin better and obtain a more uniform effect of absorbing water CA 02239~07 1998-06-04 attached, a water-absorbing agent having an average particle size of 1 to 5 ,um is preferable.
~ The silanol-condensing catalyst used in this invention includes organometallic compounds such as dibu-tyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctoate, lead naphthenate, zinc caprylate, cobalt naphthenate, tetrabutyl titanate, lead stearate, zinc stearate, cadmium stearate, barium stearate, calcium stearate and the like. The amount of the organometallic compound added is 0.01 to 0.1% by weight, preferably 0.03 to 0.07% by weight, based on the total weight of the flame-retardant, silane-crosslinked polyolefin. When the amount is less than 0.01% by weight, the crosslinking reaction does not proceed sufficiently, and when the amount is more than 0.1% by weight, crosslinking proceeds locally in an extruder when the composition is extruded and the appearance is extremely deteriorated. The sila-nol-condensing catalyst must be incorporated into the flame-retardant polyolefin. This is because when the silanol-con~n~ing catalyst is incorporated into the carrier polymer impregnated with the organic unsaturated silane or free-radical generator, the formation of an oligomer due to the condensation of the silane is accel-erated and the appearance is deteriorated.
The organic unsaturated silane used in this invention is grafted on a base resin for forming mutual crosslinking sites of the base resins. The organic unsaturated silane used in this invention is a compound CA 02239~07 1998-06-04 represented by the general formula RR'SiY2 in which R is a monovalent olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group and R' is a monovalent hydrocarbon group other than olefinically unsaturated hydrocarbon groups or is the same as Y.
It is preferable to use an organic unsaturated silane represented by the general formula RSiY3 which is the case where R' is the same as Y, and there can be used, for example, vinyltrimethoxysilane, vinyltriethoxy-silane, vinyltributoxysilane, allyltrimethoxysilane,allyltriethoxysilane and the like. The amount of the organic unsaturated silane added is 0.1 to 2g~ by weight, preferably 0.4 to 1% by weight, based on the total weight of the flame-retardant, silane-crosslinked polyolefin.
When the amount is less than 0.1% by weight, a sufficient grafting is not caused and when the amount is more than 2~ by weight, molding failure i8 caused and the process becomes uneconomical.
The free-radical generator used in this inven-2~ tion serves as an initiator for silane-grafting reaction.
The free-r~dical generator used in this invention in-cludes various organic peroxides and peresters having a strong polymerization-initiating action, and there are specifically mentioned, for example, dicumyl peroxide, a, a ~ -bis~t-butylperoxydiisopropyl)benzene, di-t-butyl peroxide, t-butylcumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)h~x~ne, t-butyl peroxypi-valate, t-butyl peroxy-2-ethylh~x~noate and the like.
CA 02239~07 1998-06-04 The amount of the free-radical generator added is 0.01 to 0.1~ by weight, preferably 0.02 to 0.05% by weight, based - on the total weight of the flame-retardant, silane-cross-linked polyolefin. When the amount is less than 0.01~ by weight, the silane-grafting reaction does not proceed sufficiently and when the amount is more than 0.1~ by weight, the extrusion-processability is deteriorated and the mold surface becomes bad.
By swelling the carrier polymer used in this invention with a li~uid mixture in which the free-radical generator is dissolved in the silane, the free-radical generator and the silane can be incorporated into the carrier polymer. At this time, for the incorporation at a high concentration, it is necessary to preheat the carrier polymer. However, the preheating must be ef-fected at a temperature not higher than the crystalline melting point so that the polymer is not melted. This is because when the preheating is effected at a temperature higher than the crystalline melting point, pellets are melted and the workability is impeded thereby.
In addition, the carrier polymer must be in the form of particles and must be a solid compatible with the flame-retardant polyolefin and the silane, The compatibility referred to herein means that the carrier polymer must not easily react with the silane and must be dispersible or soluble in the flame-retardant polyolefin.
Suitable carrier polymers are non-moisture-absorbable.
That is, it is preferable that the absorption of water is CA 02239~07 1998-06-04 relatively slow in order to m;n~m; ze the possibility of premature hydrolysis and condensation of the silane. In any case, substantially no water should be present in the carrier polymer. The carrier polymer used in this in-vention is usually in the form of granules or pellets,and pellets are preferred.
The carrier polymer used in this invention includes, for example, ethylene-ethyl acrylate copolymer (EEA~, ethylene-methyl methacrylate copolymer (EMMA), ethylene-vinyl acetate copolymer (EVA~, ethylene-propyl-ene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), a hydrogenated block copolymer obtained by hydro-genati~g a block copolymer consisting of at least one polymer block comprising mainly a vinyl aromatic compound and at least one polymer block comprising mainly a conju-gated diene compound such as hydrogenated styrene-iso-prene block copolymer (SEPS), hydrogenated styrene-buta-diene block copolymer (SEBS) or the like, and mixtures thereof.
The amount of the carrier polymer added is 1 to 5% by weight based on the total weight of the flame-retardant, silane-crosslinked polyolefin. When the amount is less than l~ by weight, no sufficient grafting is caused, and when the amount is more than 5~ by weight, molding failure is caused and the process is not ~on~m'-cal.
The flame-retardant polyolefin may, if neces-sary, have added thereto as other additives, conventional CA 02239~07 1998-06-04 additives such as antioxidant, neutralizing agent, ultra-violet absorber, antistatic agent, pigment, dispersant, viscosity improver, metal deterioration inhibitor, fungi-cide, fluidity-controlling agent and the like, and may further contain other synthetic resins.
Incidentally, in this invention, the silanol-~on~nsing catalyst is added to the base polymer; how-ever, in order to make the degree of dispersion of the silanol-condensing catalyst better, there may be used a carrier polymer other than the carrier polymer impregnat-ed with the above-mentioned organic unsaturated silane and free-radical initiator, for example, a previously melt-m;x~ mixture of a polyolefin resin with a silanol-condensing catalyst. In this case, it follows that the base polymer and two kinds of carrier polymers are intro-duced into a molding machine such as an extruder or the like in a suitable bl~n~ing proportion.
BEST MODE FOR CARRYING OUT THE INVENTION
Examples are shown below to explain this 2~ invention in more detail.
<<Production of flame-retardant polyolefin>>
According to the compounding proportions shown in Table 1, all the components shown in Table 1 were mixed and kn~A~ at a temperature of 160-180~C using a Banbury mixer to be pelletized.
<<Production of carrier polymer>>
According to the compounding proportions shown in Table 2, first of all, the carrier polymer was intro-duced into a super mixer and stirred and mixed and then preheated to 80~C. Subsequently, a liquid mixture ob-tained by dissolving a free-radical initiator in an un-saturated silane was introduced in~o a super mixer andthe carrier polymer was impregnated with the liquid mix-ture with stirring in 10 minutes.
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CA 02239~07 1998-06-04 The starting materials used were as follows:
(1) D9052: Ethylene-a-olefin copolymer/Softlex D9052 (manufactured by NIPPON OIL CO., LTD.), density: 0.905 g/cm3 ~2) P-0480: Ethylene-~-ole~in copolymer/Tafmer P-0480 (manufactured by Mitsui Petrochemical Co., Ltd.), density: 0.87 g/cm3 (3) Magnesium hydroxide: Kisuma 5B (manufactured by Kyowa Kagaku K. K.), oleic acid-treated product (4) ~uicklime (1): Average particle size: 3 ~m, stea-ric acid-treated product (5) Quicklime (2): Average particle size: 10 ~m, stearic acid treated product (6) DBTDL: Dibutyltin dilaurate (7) Antioxidant: Phenol type antioxidant/Irganox 1010 (manu~actured by Ciba Geigy) (8) Lubricant: Low-molecular weight polyethyl-ene/Sunwax 171P(manu~actured by Sanyo Kasei Kogyo K.K.) ~9) EEA: Ethylene-ethyl acrylate copolymer (EA con-tent: 23% by weight, crystalline melting point: 93~C) (10) SEPS: Hydrogenated styrene-isoprene block copolymer (styrene content: 30% by weight, crystal-line melting point: 135~C) ~11) ~-LDPE: Straight chain low-density polyethylene (density: 0.924 g/cm3, MI: 3.0 g/10 min) CA 02239~07 1998-06-04 W O97/24~01 PCT/Jr9G~'~3 (12) VTMOS: Vinyltrimethoxysilane (13) DCP: Dicumyl peroxide The evaluation methods were as follows:
(14) Amoun~ of water attached (ppm): Karl Fischer method (150~C, 30 minutes) ~ (15) Silane impregnability: VTMOS/DCP liquid mixture was heated with stirring in a super mixer and the impregnation degree at that time was evalua-ted.
o: Well impregnated, x: Impossible to impregnate (16) Extruded tape appearance: 50 mm~ extruder, 120-150-170-180-170~C, L/D: 20, Compression ratio: 3.5, Tape die: 100 mm in width, 1 mmt in lip clearance Evaluation: o > ~ > x and the level of o was deter-mined as "pass".
(17) Oxygen index: According to JIS K 7201 (18) Gel fraction (%): 120~C, 20 hours, xylene immer-sion method (19) Tensile strength (MPa) and elongation (%):
According to JIS K 6760 (20) Hot set: According to IEC-540A
o: Pass, ~: Failure The flame-retardant polyolefin obt~;n~ and the carrier polymer obt~ n~.rl were mixed in the ratio shown in Tables 3 and 4 and the mixture was extruded through an extruder and then immersed in a warm water to subject the mixture to crosslinking treatment. The resulting extruded tape was used to evaluate gel frac-tion, tensile strength, elongation and hot set. More-over, the extruded tape was pressed to be subjected to evaluation of oxygen index.
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CA 02239~07 1998-06-04 As is clear from Table 3 and Table 4, in Exam-ples l to 4, the extrusion processability was good and the crosslinking characteristics, m~r~h~n;cal characteris-tics, flame-retardancy and heat resistance were excel-5 lent.
On the other hand, in all the Comparative Examples, extrusion processability, crosslinking charac-teristics, mechanical characteristics, f~lame-retardancy and heat resistance and the like were unbalanced.
lO Industry Applicability According to this invention, it is possible to obtain a flame-retardant, silane-crosslinked polyolefin excellent in extrusion processability, and also excellent in crosslinking characteristics, m~c-h~n;cal characteris-15 tics, flame-retardancy and heat resistance.
~ PROCESS FOR PRODUCING FLAME-RETARDANT, SILANE-CROSSLINKED POLYOLEFIN
TECHNICAL FIELD
This invention relates to a silane-crosslinking process for producing a flame-retardant, silane-crosslinked polyolefin in one step using a carrier polymer cont~; n; ng an organic unsaturated silane or the like at a high concentration in the silane-crosslinking of a flame-retardant polyolefin cont~; ni ng a silanol-co~nsing catalyst and a flame-retardant.
BACKGROUND ART
In order to impart a flame-retardancy to a polyolefin composition which has been often used in coat-ing wires, cables and the like; hoses; sheets; injectionmoldings; and the like, a halogen compound and diantimony trioxide have heretofore been added to the polyolefin to achieve the flame-retardancy. However, these composi-tions are halogen-containing compositions, so that halo-gen gases, which are not only harmful in themselves butalso the cause of metal corrosion, are generated when they are burned. Therefore, these compositions have not been desired. In addition, the amount of smoke yenerated is large, the visibility b~r~ -~ bad and the people have been markedly prevented from taking refuge from a fire CA 02239~07 l998-06-04 W O 97/24401 PCT/J ~ /s4 and from fighting a fire.
In particular, from a safety aspect, it has recentl~ been strongly required that such a halogen-con-taining gas be not generated. Under such circumstances, attention has been paid to an inorganic flame-retardant using a hydrated metal compound which generates very little fumes and is very little harmful.
In recent years, a resin composite cont~ n; ng magnesium hydroxide, aluminum hydroxide or the like has been put to practical use for imparting flame-retardancy;
however, these flame-retardant resin compositions can prevent the generation of halogen-cont~i n; ng gases but have a problem in that there is caused a so-called drip ph~nom~on that the resin compositions melt and drip dur-ing the firing or in that the resin compositions areinferior in shape-ret~;n~hility at high temperatures.
In order to improve the flame-retardancy and also the heat resistance to solve the above problem, there is a method of crosslinking the resin, and this is disclosed in, for example, JP-B-57-24373, JP-B-57-26620 and the like. ~owever, the method described therein requires a large scale crosslinking apparatus for chemi-cal crosslinking, crosslinking with electron beams or the like and hence the cost of the equipment per se and the expenses for subsequent operation, mainten~nce, control and the like of the apparatus are increased, resulting in an increase of the cost of the composition. Furthermore, as stated in JP-A-60-101129 and JP-A-60-147463, in the CA 02239~07 1998-06-04 case of a flame-retardant, crosslinked composition char-acterized in that a flame-retardant is added to a silane-grafted polyolefin resin and this silane-grafted poly-ole~in resin is finally crosslinked, only the silane-grafted polyolefin resin whose crosslinking has beencontrolled has been able to be used for preventing prema-ture crosslinking in bl~A; ng and kneading the flame-retardant with the silane-grafted polyolefin resin. As a result, it has been impossible to increase the degree of crosslinking of the silane-grafted polyole~in resin and hence the heat resistance has been insufficient.
The above method requires at least two reac-tion steps, namely, the silane-grafting reaction step and the silanol-condensing reaction step. Accordingly, at least two extrusion steps must be carried out and an economical difficulty of the final product is unavoid-able.
Furthermore, the Monosil TM process method is known as a one-step process. However, this method re-quires a liquid-~AA;~g means for injecting an organic unsaturated silane in the form of a liquid into an extruder and has problems of slippage and metering fail-ure. The extruder is also required to have a large L/D
and be of an expensive and special type for uniformly dispersing a small amount of an additive, and hence, an economical problem is unavoidable. In addition, a very sophisticated technique is necessary for the extrusion and hence there have been no comm~cialized method for CA 02239~07 l998-06-04 flame-retardant type.
In addition, JP-A-3-167229 discloses, as a one-step process, a silane-crosslinking method in which a silane has been introduced into a solid carrier polymer.
However, this method uses a porous polymer or EVA as the solid carrier polymer, and in this method, in addition to the silane and the free-radical generator, an additive such as a silanol-condensing catalyst, an antioxidant or the like is also introduced into the solid carrier poly-1~ mer. Therefore, an oligomer is formed by condensation ofthe silane or the crosslinking is inhibited by trapping the radical, whereby such problems are caused that cross-linking efficiency and storability are inferior. In said Japanese publication, no flame-retardant type is men-tioned.
This invention has solved these problems andaims at providing a silane-crosslinking method comprising silane-crosslinking a flame-retardant polyolefin contain-ing a silanol-condensing catalyst and a flame-retardant, wherein a flame-retardant, silane-crosslinked polyolefin is produced in one step using a carrier polymer contain-ing an organic unsaturated silane or the like at a high concentration.
~ISCLOSURE OF T~E INVENTION
This invention is a process for producing a f~ame-retardant, silane-crosslinked polyolefin which comprises melt-mixi ng (l) a flame-retardant polyolefin CA 02239~07 1998-06-04 comprising 100 parts by weight of an a-olefin homopolymer or copolymer having a density of not more than 0.92 ~ g/cm3, 50 to 200 parts by weight of a flame-retardant, 0.5 to 10 parts by weight of a water-absorbing agent and a catalytic amount of a silanol-condensing catalyst with (2) a su~stantially water-free carrier polymer comprising a free-radical generator and an organic unsaturated silane represented by the general formula RR'SiYz in which R is a monovalent olefinically unsaturated hydro-carbon group; Y is a hydrolyzable organic group; and R'is a monovalent hydrocarbon group other than the olefinically unsaturated hydrocarbon group or the same as Y, at a higher temperature than the crystalline melting point of the base polymer of the flame-retardant polyolefin to subject them to reaction; subse~uently, contacting the reaction mixture with water to subject the reaction mixture to crosslinking. Preferably, this invention provides the above process for producing a flame-retardant, silane-crosslinked polyolefin, charac-terized in that the a-olefin homopolymer or copolymer is a homopolymer of an a-olefin such as ethylene, propylene or the like, or a crystalline, block or random copolymer of an a-olefin with at least one other a-olefins, or a copolymer of a major amount of an a-ole~in with a minor amount o~ at least one polar monomer selected from vinyl acetate, maleic anhydride, acrylic acid and the like or a mixture of them and has a density of not more than 0.92 g/cm3; the carrier polymer is a polymer selected from the CA 02239~07 1998-06-04 group consisting of an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl methacrylate copolymer (EMMA), a hydrogenated block copolymer obt~ine.~ by hydrogenating a block copolymer consisting of at least one polymer block comprising mainly a vinyl aromatic compound and at least one polymer block comprising mainly a conjugated diene compound and a mixture of them; the amount of the carrier polymer added is 1 to 5% by weight; the flame-retardant is a magnesium hydroxide or all~m;nllm hydroxide surface~treated with at least one silane-coupling agent, a silicone derivative, a fatty acid or a metal salt of a fatty acid; and the water-absorbing agent is quicklime having an average particle size of 1 to 5 ,um surface-treated with at least one silane-coupling agent, a sili-cone derivative, a fatty acid or a metal salt of a fattyacid.
This invention is explained below in detail.
The a-olefin homopolymer or copolymer used in this invention is a homopolymer of an a-olefin such as ethylene, propylene or the like; a crystalline, block or random copolymer of an a-olefin with at least one other a-olefin, for example, a crystalline propylene-ethylene block copolymer, an ethylene-butene-l random copolymer or a propylene-butene-1 random copolymer; a copolymer of a major amount of an a-olefin with a minor amount of at least one polar m~nom~ such as vinyl acetate, maleic anhydride, acrylic acid or the like (including graft copolymers); or a mixture thereof, and has a density of CA 02239~07 1998-06-04 not more than 0.92 g/cm3. When the density exceeds 0.92 g/cm3, the compatlbility of the flame-retardant with the a-olefin homopolymer or copolymer becomes inferior and the flame-retardancy b~comes low.
The flame-retardant used in this invention is a compound-having a decomposition-starting temperature in the range o~ from 150~C to 450~C and represented by the general formula MmOn-XHzO in which M is a metal, m and n are integers of l or more determined by the valency of the metal M and X is a numeral showing the crystal water content, or a double salt cont~ n ~ ng said compound Spe-cific examples of said compound include alllm;n~lm hydrox-ide (Al203-3HzO or Al(OH)3), magnesium hydroxide (MgO-HzO
or Mg(OH)z), calcium hydroxide (CaO-HzO or Ca(OH)2), bari-um hydroxide (BaO-HzO or BaO-9HzO), zirconium oxide hy-drate ~ZrO-nH20), tin oxide hydrate (SnO-H20), basic magnesium carbonate (3MgCO3-Mg(OH)z-3HzO), hydrotalcite (6MgO-A1203.HzO), dawsonite (NazCO3-Al203-nHzO) and borax (Na20-B20s.5H20), and also include zinc borate, zinc meta-borate, barium metaborate, zinc carbonate, calcium magne-sium carbonate, calcium carbonate, barium carbonate, molybdenum oxide, red phosphorus, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, ethyl diethylenephos-phate, butyl dihydroxypropylenephosphate, disodium ethyl-~ ~n~phnsphate, ~mo~; um polyphosphate, melamine phosphate, guanidine phosphate and the like. These may be used alone or in combination of two or more, and magnesium CA 02239~07 l998-06-04 hydroxide and aluminum hydroxide are preferred.
The flame-retardant is preferably one surface-treated with (i) a silane coupling agent, (ii) a silicone derivative, (iii) a fatty acid, (iv) a metal salt of a fatty acid, or the like.
The silane-coupling agent.(i) is one having, at one end of the molecule, a reactive group (methoxy group, ethoxy group, carboxyl group, cellosolve group or the like) which reacts with an inorganic material, and generally, this has a trifunctional group in many cases;
however, those having a difunctional or monofunctional group as the above reactive group may also be used. At the other end, said silane-coupling agent has a reactive group (vinyl group, epoxy group, methacryl group, amino ~ 15 group, mercapto group or the like) which chemically bonds to the resin side which is an organic material, and the skeleton of the main chain thereof is an alkoxyoligomer.
The silicone derivative (ii) is of such a type that a part of the methyl group of dimethylpolysiloxane 2~ has been replaced by various organic groups, and the various modifying organic groups include a wide variety of modifying group derivatives, for example, modifying groups for the purpose of i~ ~vlng compatibility, hydro-philic property, lubricity, water-repellency and the like such as a-methylstyrene group, ~-olefin group, polyether group, alcohol group, fluoroalkyl group and the like;
modifying groups for the purpose of il..~lovlng the reac-tivity and moisture-absorptivity such as amino group, CA 02239~07 1998-06-04 mercapto group, epoxy group, carboxyl group and the like;
modifying groups for the purpose of releasing and luster-- ing which has been substituted by a higher fatty acid, carnauba wax and an amide; and the like.
The fatty acid (iii) includes saturated and unsaturated fatty acids having 6 to 22 carbon atoms, and specifically, stearic acid and oleic acid which have 18 carbon atoms are mentioned.
The metal salt (iv) of a fatty acid includes metal soap in which the above-mentioned fatty acids are bonded to metals, and specifically, sodium stearate, potassium stearate, sodium oleate, potassium oleate and the like are mentioned. Of course, the fatty acid may be of linear chain saturated type or unsaturated type, and those in which the side chain portion is bonded to the metal are, of course, effective.
When the flame-retardant surface-treated with one of (i) to (iv) or a mixture thereof is blended in an amount of 50 parts by weight to 200 parts by weight, it is compatible with or reacts with a low crystallinity polymer having a low density, and even when a large amount thereof is blended, it is possible to easily form a composition excellent in low-temperature characteris-tics, flexibility and processability. However, when the amount is less than 50 parts by weight, the flame-retard-ing effect thereof is remarkably lowered. When the amount exceeds 200 parts by weight, the fIame-retardancy is remarkably increased, but the mechanical characteris-- CA 02239~07 1998-06-04 W O 97f24401 PCT/J~9~ 4 tics including flexibility, low-temperature characteris-tics and the like are deteriorated and the processability becomes extremely bad.
The water-absorbing agent used in this inven-tion is ~uicklime (calcium oxide), magnesium oxide, bari-_ um oxide, all~m;n~lm oxide, magnesium-al~m;nl-m-oxide, m~n~ ~ium~all lm; ~llm ~ hydroxide-carbonate, silica gel, calcium sulfate anhydride or copper sulfate anhydride.
~uicklime is preferred, and those surface-treated with the above (i) to (iv) components or a mixture thereof are more preferable. This water-absorbing agent is added to reduce the amount of water att~che~ to the flame-retar-dant polyolefin. This is because when water is attached to the flame-retardant polyolefin, premature crosslinking is caused in the silane-crosslinking step. The amount of water causing this premature crosslinking is about 100 ppm or more, and in order to control the amount of water attached to less than 100 ppm, the water-absorbing agent must be added in an amount of 0.5 to 10 parts by weight.
When the amount is less than 0 5 part by weight, the amount of water attached b~co~ 100 ppm or more and premature crosslinking is caused. Even if quicklime is used in an amount of more than 10 parts by weight, the effect of reducing the amount of water attached is not increased and rather deterioration of mechanical charac-teristics is caused in some cases. In order to make the dispersibility in the flame-retardant polyolefin better and obtain a more uniform effect of absorbing water CA 02239~07 1998-06-04 attached, a water-absorbing agent having an average particle size of 1 to 5 ,um is preferable.
~ The silanol-condensing catalyst used in this invention includes organometallic compounds such as dibu-tyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctoate, lead naphthenate, zinc caprylate, cobalt naphthenate, tetrabutyl titanate, lead stearate, zinc stearate, cadmium stearate, barium stearate, calcium stearate and the like. The amount of the organometallic compound added is 0.01 to 0.1% by weight, preferably 0.03 to 0.07% by weight, based on the total weight of the flame-retardant, silane-crosslinked polyolefin. When the amount is less than 0.01% by weight, the crosslinking reaction does not proceed sufficiently, and when the amount is more than 0.1% by weight, crosslinking proceeds locally in an extruder when the composition is extruded and the appearance is extremely deteriorated. The sila-nol-condensing catalyst must be incorporated into the flame-retardant polyolefin. This is because when the silanol-con~n~ing catalyst is incorporated into the carrier polymer impregnated with the organic unsaturated silane or free-radical generator, the formation of an oligomer due to the condensation of the silane is accel-erated and the appearance is deteriorated.
The organic unsaturated silane used in this invention is grafted on a base resin for forming mutual crosslinking sites of the base resins. The organic unsaturated silane used in this invention is a compound CA 02239~07 1998-06-04 represented by the general formula RR'SiY2 in which R is a monovalent olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group and R' is a monovalent hydrocarbon group other than olefinically unsaturated hydrocarbon groups or is the same as Y.
It is preferable to use an organic unsaturated silane represented by the general formula RSiY3 which is the case where R' is the same as Y, and there can be used, for example, vinyltrimethoxysilane, vinyltriethoxy-silane, vinyltributoxysilane, allyltrimethoxysilane,allyltriethoxysilane and the like. The amount of the organic unsaturated silane added is 0.1 to 2g~ by weight, preferably 0.4 to 1% by weight, based on the total weight of the flame-retardant, silane-crosslinked polyolefin.
When the amount is less than 0.1% by weight, a sufficient grafting is not caused and when the amount is more than 2~ by weight, molding failure i8 caused and the process becomes uneconomical.
The free-radical generator used in this inven-2~ tion serves as an initiator for silane-grafting reaction.
The free-r~dical generator used in this invention in-cludes various organic peroxides and peresters having a strong polymerization-initiating action, and there are specifically mentioned, for example, dicumyl peroxide, a, a ~ -bis~t-butylperoxydiisopropyl)benzene, di-t-butyl peroxide, t-butylcumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)h~x~ne, t-butyl peroxypi-valate, t-butyl peroxy-2-ethylh~x~noate and the like.
CA 02239~07 1998-06-04 The amount of the free-radical generator added is 0.01 to 0.1~ by weight, preferably 0.02 to 0.05% by weight, based - on the total weight of the flame-retardant, silane-cross-linked polyolefin. When the amount is less than 0.01~ by weight, the silane-grafting reaction does not proceed sufficiently and when the amount is more than 0.1~ by weight, the extrusion-processability is deteriorated and the mold surface becomes bad.
By swelling the carrier polymer used in this invention with a li~uid mixture in which the free-radical generator is dissolved in the silane, the free-radical generator and the silane can be incorporated into the carrier polymer. At this time, for the incorporation at a high concentration, it is necessary to preheat the carrier polymer. However, the preheating must be ef-fected at a temperature not higher than the crystalline melting point so that the polymer is not melted. This is because when the preheating is effected at a temperature higher than the crystalline melting point, pellets are melted and the workability is impeded thereby.
In addition, the carrier polymer must be in the form of particles and must be a solid compatible with the flame-retardant polyolefin and the silane, The compatibility referred to herein means that the carrier polymer must not easily react with the silane and must be dispersible or soluble in the flame-retardant polyolefin.
Suitable carrier polymers are non-moisture-absorbable.
That is, it is preferable that the absorption of water is CA 02239~07 1998-06-04 relatively slow in order to m;n~m; ze the possibility of premature hydrolysis and condensation of the silane. In any case, substantially no water should be present in the carrier polymer. The carrier polymer used in this in-vention is usually in the form of granules or pellets,and pellets are preferred.
The carrier polymer used in this invention includes, for example, ethylene-ethyl acrylate copolymer (EEA~, ethylene-methyl methacrylate copolymer (EMMA), ethylene-vinyl acetate copolymer (EVA~, ethylene-propyl-ene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), a hydrogenated block copolymer obtained by hydro-genati~g a block copolymer consisting of at least one polymer block comprising mainly a vinyl aromatic compound and at least one polymer block comprising mainly a conju-gated diene compound such as hydrogenated styrene-iso-prene block copolymer (SEPS), hydrogenated styrene-buta-diene block copolymer (SEBS) or the like, and mixtures thereof.
The amount of the carrier polymer added is 1 to 5% by weight based on the total weight of the flame-retardant, silane-crosslinked polyolefin. When the amount is less than l~ by weight, no sufficient grafting is caused, and when the amount is more than 5~ by weight, molding failure is caused and the process is not ~on~m'-cal.
The flame-retardant polyolefin may, if neces-sary, have added thereto as other additives, conventional CA 02239~07 1998-06-04 additives such as antioxidant, neutralizing agent, ultra-violet absorber, antistatic agent, pigment, dispersant, viscosity improver, metal deterioration inhibitor, fungi-cide, fluidity-controlling agent and the like, and may further contain other synthetic resins.
Incidentally, in this invention, the silanol-~on~nsing catalyst is added to the base polymer; how-ever, in order to make the degree of dispersion of the silanol-condensing catalyst better, there may be used a carrier polymer other than the carrier polymer impregnat-ed with the above-mentioned organic unsaturated silane and free-radical initiator, for example, a previously melt-m;x~ mixture of a polyolefin resin with a silanol-condensing catalyst. In this case, it follows that the base polymer and two kinds of carrier polymers are intro-duced into a molding machine such as an extruder or the like in a suitable bl~n~ing proportion.
BEST MODE FOR CARRYING OUT THE INVENTION
Examples are shown below to explain this 2~ invention in more detail.
<<Production of flame-retardant polyolefin>>
According to the compounding proportions shown in Table 1, all the components shown in Table 1 were mixed and kn~A~ at a temperature of 160-180~C using a Banbury mixer to be pelletized.
<<Production of carrier polymer>>
According to the compounding proportions shown in Table 2, first of all, the carrier polymer was intro-duced into a super mixer and stirred and mixed and then preheated to 80~C. Subsequently, a liquid mixture ob-tained by dissolving a free-radical initiator in an un-saturated silane was introduced in~o a super mixer andthe carrier polymer was impregnated with the liquid mix-ture with stirring in 10 minutes.
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CA 02239~07 1998-06-04 The starting materials used were as follows:
(1) D9052: Ethylene-a-olefin copolymer/Softlex D9052 (manufactured by NIPPON OIL CO., LTD.), density: 0.905 g/cm3 ~2) P-0480: Ethylene-~-ole~in copolymer/Tafmer P-0480 (manufactured by Mitsui Petrochemical Co., Ltd.), density: 0.87 g/cm3 (3) Magnesium hydroxide: Kisuma 5B (manufactured by Kyowa Kagaku K. K.), oleic acid-treated product (4) ~uicklime (1): Average particle size: 3 ~m, stea-ric acid-treated product (5) Quicklime (2): Average particle size: 10 ~m, stearic acid treated product (6) DBTDL: Dibutyltin dilaurate (7) Antioxidant: Phenol type antioxidant/Irganox 1010 (manu~actured by Ciba Geigy) (8) Lubricant: Low-molecular weight polyethyl-ene/Sunwax 171P(manu~actured by Sanyo Kasei Kogyo K.K.) ~9) EEA: Ethylene-ethyl acrylate copolymer (EA con-tent: 23% by weight, crystalline melting point: 93~C) (10) SEPS: Hydrogenated styrene-isoprene block copolymer (styrene content: 30% by weight, crystal-line melting point: 135~C) ~11) ~-LDPE: Straight chain low-density polyethylene (density: 0.924 g/cm3, MI: 3.0 g/10 min) CA 02239~07 1998-06-04 W O97/24~01 PCT/Jr9G~'~3 (12) VTMOS: Vinyltrimethoxysilane (13) DCP: Dicumyl peroxide The evaluation methods were as follows:
(14) Amoun~ of water attached (ppm): Karl Fischer method (150~C, 30 minutes) ~ (15) Silane impregnability: VTMOS/DCP liquid mixture was heated with stirring in a super mixer and the impregnation degree at that time was evalua-ted.
o: Well impregnated, x: Impossible to impregnate (16) Extruded tape appearance: 50 mm~ extruder, 120-150-170-180-170~C, L/D: 20, Compression ratio: 3.5, Tape die: 100 mm in width, 1 mmt in lip clearance Evaluation: o > ~ > x and the level of o was deter-mined as "pass".
(17) Oxygen index: According to JIS K 7201 (18) Gel fraction (%): 120~C, 20 hours, xylene immer-sion method (19) Tensile strength (MPa) and elongation (%):
According to JIS K 6760 (20) Hot set: According to IEC-540A
o: Pass, ~: Failure The flame-retardant polyolefin obt~;n~ and the carrier polymer obt~ n~.rl were mixed in the ratio shown in Tables 3 and 4 and the mixture was extruded through an extruder and then immersed in a warm water to subject the mixture to crosslinking treatment. The resulting extruded tape was used to evaluate gel frac-tion, tensile strength, elongation and hot set. More-over, the extruded tape was pressed to be subjected to evaluation of oxygen index.
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CA 02239~07 1998-06-04 As is clear from Table 3 and Table 4, in Exam-ples l to 4, the extrusion processability was good and the crosslinking characteristics, m~r~h~n;cal characteris-tics, flame-retardancy and heat resistance were excel-5 lent.
On the other hand, in all the Comparative Examples, extrusion processability, crosslinking charac-teristics, mechanical characteristics, f~lame-retardancy and heat resistance and the like were unbalanced.
lO Industry Applicability According to this invention, it is possible to obtain a flame-retardant, silane-crosslinked polyolefin excellent in extrusion processability, and also excellent in crosslinking characteristics, m~c-h~n;cal characteris-15 tics, flame-retardancy and heat resistance.
Claims (6)
1. A process for producing a flame-retardant, silane-crosslinked polyolefin, characterized by melt-mixing (1) a flame-retardant polyolefin comprising 100 parts by weight of an .alpha.-olefin homopolymer or copolymer having a density of not more that 0.92 g/cm3, 50 to 200 parts by weight of a flame-retardant, 0.5 to 10 parts by weight of a water-absorbing agent having the average particle size of 1 to 5 µm and a catalytic amount of a silanol-condensing catalyst with (2) a substantially water-free carrier polymer comprising a free-radical generator and an organic unsaturated silane represented by the general formula RR'SiY2 in which R is a monovalent, olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group and R' is a monovalent hydrocarbon group other than olefinically unsaturated hydrocarbon groups or the same as Y, at a higher temperature than the crystalline melting point of the base polymer of the flame-retardant polyolefin to subject them to reaction, and then contacting the reaction mixture with water tosubject the reaction mixture to cross-linking, wherein the carrier polymer is selected from the group consisting of an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl methacrylate copolymer (EMMA), a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block comprising mainly a vinyl aromatic compound and at least one polymer block comprising mainly a conjugated diene compound, and mixtures of them, and wherein the amount of the silanol-condensing catalyst, the carrier polymer, the organic unsaturated silane, and the free-radical generator added are 0.01 to 0.1% by weight, 1 to 5% by weight, 0.1 to 2% by weight and 0.01 to 0.1% by weight each based on the total weight of the flame-retardant, silane-crosslinked polyolefin respectively.
2. The process for producing a flame-retardant, silane-crosslinked polyolefin according to claim 1, characterized in that the .alpha.-olefin homopolymer or copolymer is a homopolymer of an .alpha.-olefin selected from the group consisting of ethylene and propylene, a crystalline, block or random copolymer of an .alpha.-olefin with at least one other .alpha.-olefin, a copolymer of an .alpha.-olefin with at least one polar monomer selected from the group consisting of vinyl acetate, maleic anhydride and acrylic acid, or a mixture thereof and has a density of not more that 0.92 g/cm3.
3. The process for producing a flame-retardant, silane-crosslinked polyolefin according to claim 1, characterized in that the flame-retardant is one surface-treated with at least one silane-coupling agent, a silicone derivative, a fatty acid or a metal of a fatty acid.
4. The process for producing a flame-retardant, silane-crosslinked polyolefin according to claim 1, characterized in that the flame-retardant is at least one member selected from the group consisting of magnesium hydroxide and aluminum hydroxide.
5. The process for producing a flame-retardant, silane-crosslinked polyolefin according to claim 1, characterized in that the water-absorbing agent is one surface-treated with at least one silane-coupling agent, a silicone derivative, a fatty acid or a metal salt of a fatty acid.
6. The process for producing a flame-retardant, silane-crosslinked polyolefin according to claim 1, characterized in that the water-absorbing agent is quicklime.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34038795 | 1995-12-27 | ||
| JP07-340387 | 1995-12-27 | ||
| PCT/JP1996/003734 WO1997024401A1 (en) | 1995-12-27 | 1996-12-20 | Process for producing flame-retardant, silane-crosslinked polyolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2239507A1 true CA2239507A1 (en) | 1997-07-10 |
Family
ID=29404525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2239507 Abandoned CA2239507A1 (en) | 1995-12-27 | 1996-12-20 | Process for producing flame-retardant, silane-crosslinked polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2239507A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115772285A (en) * | 2022-12-12 | 2023-03-10 | 云南云天化股份有限公司 | Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate |
-
1996
- 1996-12-20 CA CA 2239507 patent/CA2239507A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115772285A (en) * | 2022-12-12 | 2023-03-10 | 云南云天化股份有限公司 | Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate |
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