前苏联专利SU713535A3 Polymeric composition

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1482029 Elastomeric composition KAO SOAP CO Ltd 24 Jan 1975 [28 Jan 1974] 3165/75 Heading C3P A non-crystalline elastomeric resin composition consists essentially of a homogeneous blend of 100 parts by weight of I, a homopolymer or a copolymer (85-99À9% by weight) of vinyl chloride, and 110-160 parts by weight of II, a thermoplastic polyester-urethane; this polyester-urethane is formed by reacting an organic urethane-forming diisocyanate with a polyester diol having a M.Wt. of at least 4000 and which has been obtained by reacting a saturated aliphatic C 5 -C 8 dicarboxylic acid with a polyol component consisting essentially of a mixture of (a) 1,6-hexanediol and (b) at least one diol selected from 1,2-propane diol, n-butane 1,3-diol and C 3 - 8 diols with one or more CH 3 -side chains, the molar ratio (a) : (b) being 70 : 30-90 : 10. In the examples vinyl chloride homopolymer is blended with polyester-urethane prepared by the reaction of 4,41- diphenylmethane diisocyanate with poly-1,3- butylene/1,6-hexylene adipate. The diol (b), as well as being n-butane 1,3-diol and 1,6- hexanediol, may also be 1,2-propane diol, neopentyl glycol and trimethylpentane diol. The dicarboxylic acid, as well as being adipic acid, may also be pimelic, suberic or methyl-adipic acids.
公开号:SU713535A3
申请号:SU752104686
申请日:1975-01-27
公开日:1980-01-30
发明作者:Казама Еситеру；Миура Ясуо；Сузуки Юдзи；Игучи Казуо；Кавабучи Кендзи
申请人:Као Соуп Ко,Лтд (Фирма)；
IPC主号:

专利说明:

(54) POLYMER COMPOSITION
glycol, b3-bupylene glycol, greg-butyl glycol and trimethylpentanediol.
As a saturated aliphatic dicarboxylic acid containing from 5 to 8 carbon atoms, glutaric acid, adipic acid, pimelic acid, corky acid and methyl adipic acid can be used. Environmentally preferably using adipic acid.
It is important that the molecular weight of a polyester derived from 1,6-hexanediol, a low molecular weight dyod containing a methyl group in the side chain, and a saturated aliphatic carcass containing 5–8 carbon atoms is equal to at least 4000. The upper limit of a mole, of a specific weight is not critical, and can be a factor of up to about 20,000. If the molecular weight is less than 4,000, the rubber-like elasticity is reduced, expressed by the elasticity limit. The preferred range of molecular webs is 6000-10000.
Vinyl polymer biased with thermoplastic polyetherurethane: includes vinyl chloride homopolymers and 1-vinyl chloride copolymers containing from 85 to 99.9 wt. % vinyl chloride, and the remainder, i.e., from 0.1 to 15 weight. % represents one lly of more monomers copolymerizable with vinyl chloride. As monomers copolymerizable with vinyl chloride, vinyl acetate, vinylidene chloride, acrylonitrile, diethyl maleate, dibutyl maleate, diethyl fumarate, and acrylic and methacrylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, methacrylate, and methacrylate can be used. In general, vinyl chloride homopolymers are more widely used in industry than vinyl chloride copolymers, and therefore homopolymers are more often used in practice.
The degree of polymerization of the vinyl chloride polymer is practically not critical, but it is generally preferred that its degree is polymeric. The mea- surements are at least 600, and as a result of the higher degrees of polymerization, the composition offered is more elastic.
The upper limit of the degree of polymerization is not cr, it is a critical factor and can be equal to about 3000.
The preparation of a resin composition from said thermoplastic polyetherurethane and vinyl chloride polymer is carried out by mixing both resin components in a predetermined weight ratio using a vertical or horizontal mixer, usually used for mixing resin-like materials, and
then heating, homogenizing and plasticizing the pre-blend obtained in a discontinuous or continuous manner using a mixing
calender, intermediate mixer and plasticizing extruder. It is possible to heat and heat | Stimulate both components directly without preparing a preliminary mixture. In addition, in order
In order to decrease thermal decomposition of vinyl chloride polymer, a heat stabilizer can be added to the resin composition. In addition to the stabilizer, ingredients such as fillers, colorants, softeners, plasticizers, etc. can be added to the table. The amount of these additional ingredients can be chosen according to accepted recipes. The composition according to the invention may be
used to form articles from it that must have rubber-like elastic properties, such as films, sheets, synthetic leathers, belts, pipes, hoses, and packages, using the various molding methods used. In addition, the composition can be widely used in various fields of technology for forming parts for the electrical industry, e.g.
wires, as well as powdered adhesives for layout engineering, etc., and as shoe alloys, obtained (Methods lnt under pressure, etc.)
The physical properties indicated in the examples were evaluated according to the following methods.
1. Elasticity by rebound.
Rebound elasticity was determined at 25 ± 10 ° C using a Shoba elastomer. A sample with a thickness of 6 ± 1 mm was obtained by connecting 6 sheets with a thickness of approximately 1 mm, and rebound elasticity (%) was measured by adjusting the thickness depending on the height of the dip (trough. Measured value obtained value X (11) 5 + 5)
(in case of a tumbling fall from a height of 25 cm.
Measure my value obtained valueX (15) 5 + 9)
(in case of tilting from a height of 1.2.5 cm).
In the above formula 5 indicates the actual thickness of the sample.
2. The temperature is 10B1an.i (° C). Zoeoelasticity was measured on the spectrum of the rometer in; 31 elasticity of n; ro: of (water (Ivamoto svaakasho guva, and the temperature of glass) (° C) was estimated at its maximum tg6, and observed when temperature changes.
3. Modules at 100% stretching (k.).
According to the test method for tensile strength I / S K-6723, a tensile stress of 100% was determined at an elongation rate of 200 mm / min, and a certain value was considered as a modulus at 100% stretch.
4. Strength limit (kg / szh).
The ultimate strength was determined in accordance with the I / S K-6723 test method using an autograph made by Shimatsu Sisakasho.
5.Time change ratio - {%).
In accordance with the test method of strength K-6723, the modules of extension and stretch by 50% were determined at a stretching rate of 50 mm / min. The temporal change coefficient was calculated using the following formula:
Coefficient (%) of time variation
-thirty
--huyo
NO
where EI is the modulus at 50% stretch, determined 1 day after molding;
EZO .- modulus at 50% stretch, determined 1 st 30 days after molding.
Example 1. 200 parts of poly-1,3-butylene (hexylene) adnpata, characterized by throxyl CHI1SL | 0M 17.8 (mol. Weight. 6300), which is obtained from a polyol component containing 1,6-hexanediol and 1,3- butylene glycol in a molar ratio of 80:20 and adipic acid, heated at 80 ° C, 8 parts of 4,4-diphenylmethane diisocyanate are added and the mixture is intensively transferred for 3 minutes to obtain a homogeneous mixture. The mixture is then left to mature at 140 ° C for 3 hours under a nitrogen atmosphere to complete the urethane formation reaction. Thus, polyether urethane 1 is obtained.
- Separately. 100 parts of polyvinyl chloride having a degree of polymerization of 1050, 08 parts of calcium stearate and 1.2 parts of stearathia are subjected to kneading on hot rollers maintained at a temperature of 160 ° C for 5 minutes. Then, 120 parts of the previously obtained polyetherurethane I are gradually added to the kneaded mixture, and the mixture is kneaded for 10 minutes until a homogeneous composition is formed. The pelt thus obtained with a thickness of approximately 1.2 mm is pressed under a pressure of 60 kg / cm for 5 minutes on a hot press heated to a temperature of 165 ° C. Elasticity, glass temperature (important, tensile strength and coefficient of change over time measured for a molded article obtained from a polymer mixture prepared in this manner.
The following results were obtained:
Elasticity,% 11.7
Glass transition temperature, ° C-3
Module 100%, kg / cm 33
Strength, kg / cm 206
chime,% 37
Example 2. 200 parts of poly-1,3-butylene (hexylene) adipate, characterized by a hydroxyl number of 14.2 (mol. Weight 7900), which is obtained from a polyol component consisting of 1,6-hexanediol
and 1,3-butyl.nglpcol, in a molar ratio of 87: 13, and adipic acid, are heated at 80 ° C, then 6.4 parts of 4,4-diphenylmethane diisocyanate are added and the mixture is stirred vigorously
within 3 minutes to form a homogeneous mixture. The mixture is then allowed to mature for 3 hours at 140 ° C under a nitrogen atmosphere until the urethane formation reaction is complete. As a result of this, polyetherurethane (P) is obtained.
Separately, 100 parts of polyvinyl chloride having a degree of polymerization of 1050, 0.8 parts of calcium stearate and 1.2 parts of zinc stearate are kneaded on hot rollers for 5 minutes at a temperature of 160 ° C. Then 120 parts of the resulting polyetherurethane are gradually added to the kneaded mixture And, the resulting mixture was kneaded at 160 ° C for 10 minutes to form a homogeneous composition. The pelt thus obtained with a thickness of approximately 1.2 mm is pressed in at a pressure of 60 kg1 cm.
5 minutes at the time than the dress, heated to a temperature of 165 ° C.,
The physical properties of the molded article obtained from the prepared polymer mixture are determined.
Get the following results:
Elasticity,% 14 Glassmaking Temperature, ° C-4
Module 100% -, ny,. kg1cm 34
Strength, kg1cm 328 Coefficient of change
in time,% 77
Example 3. The molded article was prepared using the method of Example 1 from a polymer (opion plate), similar to the product obtained in Example 1, but changing the molar ratio of 1.6hexanediol and 1,3-butylene glycol and the molecular weight of poly-1,3 -butylene (hexylene) adipate.
The results of the experiments are shown on the thus obtained plates are presented in table. one.
For comparison, a plate is prepared in a similar manner using a polyol component, in which the indicated molar ratio lies outside the α-proposed range (an example based on prior art), and another plate is prepared using only 1,6-hexanediol as the polyol component. (comparative example), and these plassins are subjected to tests, the results of which are presented in Table. one.
Table 1
Example 4. 200 parts of poly-1,3-butylene (hexylene) adipate, characterized by a hydroxyl number of 20.4 and mol. weighing 5,500, obtained from a polyol component containing 1,6-hexanediol and 1,3-butylene glycol in a molar ratio of 90: 10, and adipic acid, is heated to 80 ° C, and then 6.4 parts of 4.4- diphenylmethane diisocyanate and the mixture is vigorously stirred for 3 minutes until a homogeneous mixture is formed. The mixture is then allowed to mature ori 140 ° C for 3 hours under a nitrogen atmosphere until the urethane formation reaction is complete. Get floor ether ether (P1). Separately, 100 parts of polyvinyl chloride, 0.8 parts of calcium stearate, and 1.2 parts of zinc stearate are plastered for 5 minutes on hot crushers heated to 160 ° C. Then 120 parts of the specified polyol | retane P1 are gradually added to the plasticized mixture. and the resulting mixture is plastered for 10 minutes at 160 ° C until a homogeneous mixture is formed. The pelt thus obtained with a thickness of 1.2 mm is pressed at pressures of 60 kg / cm for 5 minutes on a hot press heated to 165 ° C. The physical properties of the molded product are determined from the polymer mixture obtained in this way. The following results were obtained. Elasticity,% 12.7 Glass Temperature, ° C-3 Module 100%, kg / cm Limit of Impact, kg / cm Comparative Example. In Example 4, a molded plate was prepared, except that instead of 120 parts of polyetherurethane used in Example 4, 120 parts of an industrial thermoplastic polyether insert were used for mixing with polyvinylchloride resins. The physical properties of the molded sheet are determined. The following results were obtained: Elasticity,% Glass transition temperature, ° С Module IQO%, kg / sl1 tensile strength, kg / cm 186 P p –i m 5 5. 100 parts of polyvinyl chloride, 0.8 parts of calcium stearate and 1.2 parts Zinc stearate is mixed in a crusher, which is accompanied by heating to 180 ° C for 5 minutes. 120 parts specified in the table. 2 polyether portions are added to it and mixing is continued at the same temperature for another 10 minutes, until it becomes uniform. The sheets obtained in this way are about 1.2 mm thick pressed at a temperature of 165 ° C and a pressure of 60 kg / cm for 5 minutes to obtain a test sheet about 1 mm thick., /. The results are presented in table. 2
Example 6. The analysis of polyester is presented in Table. 3. Note. Polymer blend sheets are prepared in Example 5.

权利要求:
Claims (1)
[1]
Invention Formula
Polymer composition, including polyvinyl chloride and polyurethane, characterized in that, 1C aims to improve the physicomechanical properties of the composition, as polyurethane, it contains poly1 Detanum on the basis of 4,4-diphenylmethanedi isocyanate and polyether with mol. weight. 6000 - 10,000, obtained by condensation of a saturated aliphatic dicarboxylic acid Sb-GS with a mixture of 1,6-hexanediol and a diol containing 3-8 carbon atoms and having one methyl side group, taking table 2
Table 3
in the ratio of 70: 30-90: 10 in the following ratio of components of the composition, wt. including:
100
Polyvinyl chloride 110-160 Polyurethane
Sources of information taken into account in the examination:
1. US Patent: No. 3381056, cl. 260-859,1969.
5 .. US Patent No. 34871.26, cl. 260-859, 1969 (prototype). using the same method that is described

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同族专利:

公开号 | 公开日

JPS50111152A|1975-09-01|

FR2259135B1|1978-03-10|

JPS5345234B2|1978-12-05|

GB1482029A|1977-08-03|

DE2502638A1|1975-07-31|

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US3984493A|1976-10-05|

引用文献:

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RU2541529C2|2009-11-26|2015-02-20|Басф Се|Method of producing polymers using 1,6-hexanediol containing less than 500 ppm of aldehyde|BE568857A|1957-06-26|

DE1193241B|1963-03-13|1965-05-20|Bayer Ag|Process for the production of homogeneous, thermoplastic and highly elastic plastics from inert vinyl polymers and polyurethanes|

US3381056A|1965-08-23|1968-04-30|Monsanto Co|Polyblends comprising a vinyl chloride graft copolymer, a polyester urethane elastomer and vinyl polymer|

US3467731A|1967-04-11|1969-09-16|Union Carbide Corp|Vinyl coating compositions of polyvinyl chloride of 2,2-dimethyl-1,3-propanediol mono|

DE1802471A1|1968-10-11|1970-05-14|Bayer Ag|Process for the production of homogeneous, thermoplastic and highly elastic plastics from vinyl chloride polymers and polyurethanes|

US3763054A|1970-12-07|1973-10-02|Bayer Ag|Process for the production of microporous polyurethane sheet structures permeable to water vapor|

US3718622A|1970-12-31|1973-02-27|Hooker Chemical Corp|Gel prevention in polyurethanes|

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US4212957A|1977-12-27|1980-07-15|Monsanto Company|Plastifiers, method of preparation and PVC compositions containing same|

US4350792A|1979-03-01|1982-09-21|Stauffer Chemical Company|Blend of internally plasticized vinyl chloride copolymer and polyurethane elastomer|

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GB2262940A|1991-12-23|1993-07-07|Amtico Co|Floor coverings|

CA2166122A1|1993-06-25|1995-01-05|William H. Mann|Thermoplastic urethane elastomeric alloys|

US5965650A|1997-10-07|1999-10-12|Ludlow Composites Corporation|Floor coverings|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

JP1170674A|JPS5345234B2|1974-01-28|1974-01-28|

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