SU713534A3 - Thermoplastic molding composition - Google Patents

Description

but sizes and with good appearance.

The aim of the present invention is to improve the unavailable network and the appearance of the products prepared from it.

This goal is accomplished by adding an additional oil holder — polymers or alpha olefipes — with lower thermal fluidity than a basic resin insoluble in lubricating oil and absorbing O-3.0% oil of its own weight at 18–25 ° C and soluble in oil or absorbing into the composition. at least 30.07 o of its own weight oil at a temperature exceeding by 10 ° C the temperature of fluidity of the resin of the main character; moreover, the resin is similar to an oil holder at 18–25 ° C and at A temperature exceeding by 10 ° C the temperature of the resin flow absorbs O-50 wt. % oil absorbed by the oil holder (with the following ratio of comonents, weight,%:

Lubricant0,2-25

Oil holder 0.1 -12.5

Resin main

the nature of the rest

Trie weight ratio of oil to the oil holder from 2: 1 to 15: 1.

The oil holder according to the invention is a thermoplastic resin with a low yield point, which remains undissolved in oil at normal room temperature and absorbs no more than 0.03 times its own weight (not more than 0.03-1 from the point of weight ratio) oil to the oil holder). It does not dissipate oil or absorbs it in an amount not less than 0.3-fold of its own weight, i.e. not less than 0.3-1 in relation to the weight ratio of oil to oil holder at a temperature higher by 10 ° C than the pour point of the resin of the main character. In addition, it should begin to separate the oil when the temperature drops to room temperature.

Pour point is the temperature at which this resin begins to melt and flow out of the extruder plastometer orifice with an orifice of 1 mm and a length of 30 mm when heated at a constant rate as the temperature rises by 3 C / min under a pressure of 50 kg / cm.

Oil retention properties. The resins are identified as follows.

A test sample of a resin with a thickness of 1 mm and a weight of 1 g should remain undissolved in oil and absorb oil in an amount of 0.03-1 times, based on the weight ratio of oil to oil holder after keeping the oil at normal room temperature for 5 days. When the test specimens with a thickness of 1 mm and a weight of 1 i are kept in the oil and the temperature is above 10 ° C, the flow temperature of the basic resin for 5 hours must be dissolved in the oil or absorbed by it in an amount of at least 0.3- 1-fold, and based on the weight ratio of oil to the oil holder.

The basic resin is a thermoplastic resin, remaining with non-solvent in oil and absorbing no more than 0.03 times the amount of oil by weight of the oil (i.e. not exceeding 0.03-I times, calculated on the basis of the weight ratio of oil to c. mole of the main character). In addition, it is necessary that at a temperature of 10 ° C higher than the flow temperature of the resin of the main character, this resin absorbs oil in an amount not exceeding half the weight of oil absorbed by the oil holder.

The amount of oil that the basic resin absorbs at normal room temperature is determined under the same conditions as in the case of an oil holder. This basic resin is required to absorb oil in an amount not exceeding 0.03 to 1 fold, based on the weight ratio of the oil to the basic resin. The amount of oil absorbed by the resin of the main character of irn temperaure, exceeding by temperature, the resins of the main xapaKi.pn, measured in the same areas as in the case of the oil retainer, should be less than 0.5, preferably 0.25, preferably 0, 1 of the amount of maela that absorbs the oil holder under the same conditions.

The oil for the purposes of the invention is a lubricating oil, liquid at normal room temperature, which, although it is solid at normal room temperature, decreases at a temperature below the flow temperature of the basic resin. Lubricant satisfies this requirement.

Examples of compounds used as an oil retainer of the invention are polyethylene, polypropylene, polybutene and poly-4-methylpentene-1.

Examples of compounds used as the main resins of the invention are:

a half-acetal resin, for example, a homopolymer polyoxymethylene, a copolymer of formaldehyde, trioxane, tetraoxane, and not more than 20 mol. % cyclic simple ether containing up to 8 atoms of ztlerod; polyamide resin, for example, polyhexamethylethylene adipamide, polycaprolactam, ioligexamethylene sebacamide, complete minonec-decanoic acid, poly-alaurolactam, a product of condensation polymerization of terephthalic acid and trimethylhexamethylene diamide;

polyester resin, for example polybutylene terephthalate, polyethylene terephthalate. a copolymer of 1,4-cyclohexylenedimethylene terephthalate and isophthalate, polyethylene, 2-diphenoxymethane-4, 4-dicarboxylate, polybutylene terephthalate, containing not more than 5 mol. % tetrabromobisphenol L as comonomer;

polycarbonate resin, for example aromatic polycarbonate;

full vinyl chloride resin, for example, a full vinyl chloride homopolymer, a copolymer of vnnichloride and no more than 20 mol. 7o vinyl acetate, a copolymer of vinyl chloride and not more than 20 mol. % propylene, a copolymer of vinyl chloride and not more than 20 mol. % (total) of ethylene and vinyl acetate;

polystyrene resin, for example, homopolymer polystyrene, styrene sonolymer with not more than 20 mol. % methyl methacrylate, styrene sonolimer with not more than 20 mol. % a-methylstnrol; acrylic resin, for example, polymethyl methacrylate, methyl methacrylate copolymer and no more than 20 mol. % a-methylstyrene, a copolymer of methyl methacrylate and not more than 20 mol. % ethyl methacrylate, a copolymer of methyl methacrylate n not more than 20 mol. % n-butyl methacrylate;

fluorocarbon resin, such as polpmonochlorotrifluoroethylene, polyvinylidene fluoride, a copolymer of tetrafluoroethylene and 15-25 weight. % hexafluoropropylene, polytetrafluoroethylene-containing perfluoroalkoxy chain, copolymer of tetrafluoroethylene and ethylene;

polyphenlenoxide, for example polyphenylene oxide, modified polyphenylene oxide, containing 40-60 weight. % polystyrene;

polyphenylene sulphide resin;

polysulfone resin;

polyarnsulfone resin; polyaryl ester resin;

polyester sulfone resin;

polyvinyl formal resin;

polyvinyl butyral resin;

acrylonitrile resin;

acrylonitrile resin-butadiene resin.

These resins can be used in the form of copolymers with no more than 20 mol% incorporated into them. % copolymerizable monomers.

Of these resins, polyacetal resins, polyamide resins, ester resins, polycarbonate resins and polyphenylene oxide resins are particularly desirable.

Examples of oils used in connection with parathin are paraffinic, naphthenic, aromatic and other hydrocarbon oils, alkyl esters and other oily esters, and glycol oils. Of these oils, hydrocarbon oils and ester-based oils are particularly desirable. According to the invention, a combination is necessary.

the three components, i.e. the oil holders, the resins of the main character and the oils, as described above. Usually, the ting oil of the holder and the resin of the main character, effective at combination, are varied in

depending on the particular type of oil chosen.

For example, when using an iaraffin or naphthenic oil, it is advisable to use a polyolefin or monomer as an oil retainer, and as the main resin it is desirable to use one or more resins selected from a polyacetal resin, a polyester resin, a polycarbonate resin , polyvinyl chloride resin, copolymer of acrylonitrile and styrene, acrylic resin, fluorocarbon resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyarshl l foiovoy resin poliarilefirnoy S1moly, poliefirsulfopovoy resin nolivinilformalevoy and polyvinyl butyral resins, particularly preferable combination of components provides the use narafinovogo or naphthene oil as a lubricating oil, polyethylene or polypropylene as maslouderzhivatel and one or more resins,

selected from a polyacetal resin, a polyamide resin, a polyester resin, a polycarbonate resin, and a polyphenylene oxide resin as the main resin.

When choosing an aromatic oil as a lubricating oil, it is desirable to use a polyolefin, monomer or polystyrene as an oil holder, and one or more resins selected from a polyacetal resin, a nolyamide resin, a polyester resin, and a hydrofluorocarbon resin are desirable to use as the base oil.

When choosing an ester-based oil as a lubricating oil, it is desirable to use polyolefin or ionomer as the oil retainer, and one

or several resins selected from polyacetal resin, polyamide resin, polyester resin, acrylonitrile / styrene copolymer, acrylonitrile copolymer, styrene and butadiene, fluorocarbon resin, phenylene oxide resin. polyphenylene sulphide resin, polysulfone resin, polysulfuric resin, polyarylether resin and polyethersulfone resin, in particular, when using an eppra-based oil as a lubricant oil, the preferred combination of components is obtained by using polyethylene or polyproylleppe as a base oil as a lubricant oil as a lubricant oil; , polyamide resin, polyester resin or polyphenylene oxide resin. The ratios of the three components of the composition, i.e., oils, oil holders and resins, are also essential to achieve the full ester of the invention. The amount of oil retainer in the composition should be in the range of 0.1-12.5 weight. % When used, an oil holder in an amount exceeding the upper limit weakens the properties imparted by the base resin. When using oil holders in an amount of less than 0.1 weight. The% effect of the invention becomes insignificant. A more desirable range of oil retainer is 0.5-10 weight. %, preferably 1-5 wt. % The amount of oil in the composition should be in the range from 0.2 to 25 weight. % When using oil in excess of the upper limit, the oil is hardly immobilized with the resin and the properties imparted by the basic resin are weakened. When using oil in less than 0.2 wt. % reported lubricating properties are low. A more desirable oil amount range is 1-20 wt. %, preferably 3-13 wt. % The amount of basic resin in the composition should be between 99.7 and 50 wt.%. %, preferably 98.5 to 70 weight. % preferably 96-80 weight. % In addition, the required weight ratio of oil to oil holder is in the range from 2.0: 1 to 15: 1. At a ratio greater than 15: 1, the oil content becomes too large to allow the components to mix normally. However, if this ratio is less than 2.0: 1, the resulting composition suffers from insufficient lubricating capacity. More optimal weight ratio from 3: 1 to 12: 1. The oil retainer agent and the base resin to oil are also essential in accordance with the invention. The resin serving as an oil holder should have such properties that the test sample of a resin with a thickness of 1 mm and a weight of 1 g does not dissolve in oil, does not absorb oil in excess of 0.03-1, in the calculation of ira weight ratio of oil to oil extractor , if kept in oil at normal room temperature for 5 days. If the oil retainer absorbs the oil in an amount exceeding 1 o'clock, we eat this value, then the absorbed oil at elevated temperatures hardly separates from the oil retainer at normal room temperature. A more desirable upper limit of absorbable oil is 0.01-1, based on the weight ratio indicated. If the test sample of the resin is held for 5 h in maele at a temperature exceeding JUS, the flow temperature of the resin is of a new nature, it is necessary that the oil should be dissolved or absorbed in an amount not less than 0.3-1, calculated on the basis of the weight ratio to the oil holder. When the value is below the lower limit of 0.3-1, the amount of absorbed oil will not be sufficient to provide the desired lubricity. A more desirable lower limit of the ratio is 1. It is also required that the flow temperature of the oil holder is lower than that for an resin of an axial character. If the pour point of the oil holder is higher than the primary temperature of the resin, it is not possible to obtain a satisfactory dispersion of the oil and the oil holder. It is necessary that the resin (when it is wasted in such areas as when testing the oil holder) absorbs oil in an amount not exceeding 0.03-1, calculated on the basis of the weight of weight of the resin to the basic character at normal temperature at room temperature. If the resin of the main character absorbs oil in an amount lying near this interval, then the emol of the main character tends to be too soft. A more desirable upper limit of the ratio is 0.01-1, and preferably 0.005-1. The amount of oil that absorbs an emol of a basic nature at a temperature of 10 ° C above the pour point, determined under the same conditions as for the oil retainer, should be less than 0.5, preferably less than 0.25, better than 0.1 of the amount of oil absorbed by the oil holder. Behind these limits, you increase the distribution of oil in the resin of the main character; the expected effect of the oil holder decreases. The composition of the invention, in accordance with the above values, has well-balanced properties with respect to lubricity and formability. It also has high discernability and gives precise dimensions, the composition can be molded into molded products that are non-sticky and have a good appearance.

Various additives can be incorporated into the composition, although this is not necessary. For example, solid lubricants such as graphite, molybdenum disulfide, powdered teflon, boron nitride can be added to the composition to meet individual requirements; inorganic powdered fillers, for example talc, calcium carbonate, kaolin, glass powder, glass beads and microspherical glass particles, inorganic fibrous reinforcing agents, for example glass fiber, carbon fiber and asbestos, powdered metals, for example aluminum iron and copper powders; metal fibers; for example wool stainless steel.

Various methods are used to prepare the compositions of the invention.

For example, the composition can be prepared by simultaneously heating, mixing and kneading three components, i.e., an oil holder, a basic resin and an oil, mixing the oil holder and an oil, and then adding the basic salt to the mixture, adding the oil either during or after basic character with an oil holder, the introduction of an oil holder or during or after mixing the resin of the main character with the oil. Mixing order, heating method and other conditions are selected depending on specific requirements.

Devices commonly used for mixing or kneading may be used.

From a technological point of view, it is desirable that the oil holder and the basic resin used as the raw material for the composition of the invention be in a finely divided state with a particle size passing through a 10-mesh sieve. Such raw materials can be effectively used even in the form of small balls.

This invention is described in the following examples, which are illustrative and do not limit the invention.

Examples 1-6, 10-83. In the calsdom of these examples, the basic resin, oil holder and oil are mixed in various amounts corresponding to the above ratio (total about 5 kg) for 10 minutes using heat in a 20 liter Henshel mixer (apparatus for mixing liquids with high speed) at a temperature below the fluid temperature of the oil holder and the ratio of components so that the oil holder cannot dissolve or adhere to the mixer. The resulting mixture

Grays} is molded using a curved extruder of myoaxial (shaft diameter 40 mm, ratio VB 28). The resultant molded particles are plasticized using a screw-type injection molding machine (50 Z). Cylindrical test specimens are prepared from three molded particles using an injection molding machine of the screw type (50 Z). These

The test specimens are subjected to a friction test using a friction test device (Suzuki model) with a weight of 2 kg; cm2 with a linear viscosity of 1 cm / s and a ratio of resin to steel grade S45C.

Separately, the resin of the main character and the oil holder are molded separately in a commission molding machine with the formation of flat sheets with a thickness of 1 mm. The test piece weighing 1 g is cut into flat sheets. Each test sample is immersed in oil for 5 days at room temperature. Thereafter, in the test samples, the

content of absorbed oil. The weight ratios of the absorbed oil to the oil holder are determined and recorded as the absorption values of the oil in the corresponding resins at room temperature.

temperature

The same samples, as used to determine the absorption of oils at room temperature, are kept in oil for 5 hours at temperatures above the pour point of the main resin. Thereafter, the absorbability of the oil in the test samples is determined. The weight ratios of the absorbed oil to the base resin are determined and recorded as the absorption values of the oils in the respective resins at elevated temperature. When the test samples are dissolved in oil, the weight ratio is expressed as infinity.

After determining the absorption of the oils at elevated temperature, the ability of the oil retainer to retain the oil is assessed by visual observation.

Such an ability is assessed on a scale with which the range, degree, and degree of power indicate the corresponding degrees of oil sweating. The pour point is determined by applying a sample of a resin weighing 2 g on a Coken flow tester.

Examples 7-9. In each of these examples, the resin of the main character is mixed and the oil holder is in different

quantities satisfying given

ratios (about 20 kg in total) in terms of 20 missions at a room temperature 50-liter ribbon mixer (lirath for mixing with CKor / ocTbif)).

The resulting mixture is extruded with lijii; a variable monoaxial extruder with an outlet (shaft diameter 65 mm). In the case of extrusion, a predetermined amount of the oil is injected into the molten resin under pressure, which exceeds the pressure of the molten resin and the mixture is molded into small pieces.

The resulting molded particles are plasticized using a worm-type injection molding machine (50 Z). From such molded particles, test pieces of cylindrical shape are produced with the use of a worm-type injection molding machine (50 Z). These test specimens are subjected to friction testing using a impact impact tool for friction testing (Suzuki model) and a fixed load of 2 kg / s with a linear viscosity of 1 cm / s at a ratio of resin to steel grade S45C.

The resin of the main character and the mold holder are molded separately in a compression molding machine with the formation of silt sheets 1 mm thick. A weighable piece weighing 1 g is cut into flat sheets. Each test sample is immersed in oil for 5 days at room temperature. Thereafter, the content of absorbed oil is determined in the test samples. Determine the ratio of absorbed oil to masticator n is recorded as the oil absorption values in the respective resins of the nrn room temperature.

The same samples, as used to determine the absorption of oils at room temperature, are kept in oil for 5 hours at a temperature of 10 ° C above the flow temperature of the main resin. Thereafter, the absorbable oils in the test specimens are determined. The weight ratios of the absorbed oil in the resin of the main character are determined and measured as the absorption values of the oils in the respective resins and elevated temperatures. When the test samples are dissolved in oil, the weight ratio is expressed in infinity.

After determining abeorbcin oils at elevated temperatures, the ability of the oil holder to hold the oil is assessed by visual observation. Such an ability is assessed but on a tibal scale in which the wall is strong, medium, and weak, indicates the appropriate degree of oil sweating.

The pour point is determined using a sample of this resin weighing 2 g of a Coken flow tester.

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As the basic resins, oil holders, oils, and additives used in these examples, the compounds listed below are used as irides.

Resins of the main character.

Polyoxymethylene 1: polyoxymethylene homopolymer. Ml-13, for injection molding.

Polyoxymethylene 2: a copolymer of formaldehyde, trioxane, tetraoxane and not more than 20 mol% cyclic nonster ether, containing up to 8 carbon atoms, MI-9, for injection molding.

Polyamide 1: polyhexamethylene adipamide, viscosity in sulfuric acid 2.5, for injection molding.

Polyamide 2: poly-E-canrolactam, sulfuric acid viscosity, about 2.7 for lower forming.

Polyamide 3: nolhexamethylene sebacamide, viscosity in sulfuric acid 2.6 for injection molding.

Polyamide 4: full moon-nlekanic acid, viscosity in sulfuric acid 2.4 for injection molding.

Polyamide 5: zolayurolactam, viscous in sulfuric acid 2.4 for injection molding.

Polyamide 6: a condensation product and terephthalic acid and trimethylhexamethylenediamine, and a viscosity in sulfuric acid of 2.5 for injection molding.

Polyester 1: polybutylene terephthalate, solution viscosity 1.2 for injection molding.

Polyester 2: polyethylene teref; and chat, viscosity in solution 1.2 for injection molding.

Polyester 3: 1,4-cyclohexylenedimethylene terephthalate co-polymer and isophthalate, viscosity in solution 1.2 for injection molding.

Polyester 4: polyethylene-1,2-diphenokeethanol-4, 4-dicarboxylate, viscosity in solution 1.2 for injection molding.

Polyester 5: nolybutylene terephthalate containing no more than 5 mol. % tetrabromobiephenol A, viscosity in solution 1.2 for injection molding.

Polycarbonate: aromatic polycarbonate, with an average molecular weight of 25,000 for injection molding.

Polyvinyl chloride 1: polyvinyl chloride homopolymer, polymerization wall 800.

Polyvinyl chloride 2: vinyl chloride copolymer of not more than 20 mol. % vinyl acetate, the average degree of polymerization of 1.100.

Polyvinyl chloride 3: vinyl chloride coiolimer and no more than 20 mol. % propylene, average degree of polymerization 800.

Polyvinyl chloride 4: vinyl coiolimer13

chloride and ge more than 20 mol. 7% (total) of ethylene and ninil acetate are the average degree of imerimerization 1000.

Polystyrene 1: polystyrene homo-polymer for injection molding.

Polystyrene 2: styrene copolymer and no more than 20 mol. % methyl methacrylate for injection molding.

Polystyrene 3: styrene coiolimer and not more than 20 mol. % a methylmestrol for injection molding ..

Acrylic resin 1: polymethyl methacrylate for injection molding.

Acrylic resin 2: methyl methacrylate soiolimer and not more than 20 mol. % a-methylstyrene for injection molding.

Acrylic resin 3: methyl methacrylate copolymer and not more than 20 mol. % ethyl methacrylate for injection molding.

Acrylic resin 4: Methyl methacrylate sonolimer and not more than 20 mol. % n-butyl methacrylate for injection molding.

Fluorocarbon resin 1: polyammonochlorotfluoroethylenes for injection molding.

Fluorocarbon resin 2: inorganic vinylidene fluoride for injection molding.

Hydrofluorocarbon resin 3; tetrafluoroethylene copolymer and 15-25 wt. % hexafluoropropylene for injection molding.

Fluorocarbon resin 4: polytetrafluoroethylene containing a perfluoroalkoxylic side chain for injection molding.

Fluorocarbon resin 5: tetrafluoroethylene and ethylene sonolymer for injection molding.

Polyphenylene oxide 1: polyphenylene oxide for injection molding. Polyphenylenoxind 2: modified phenol-ileoxide, containing 40-60 weight. % styrene for injection molding.

Polyphenylene lipid: for injection molding.

Polysulfone: for injection molding.

Polyarylsulfone: for injection molding.

Polyaryl ether: for injection molding.

Polyethersulfone: for injection molding.

Polyvinyl formal: for injection molding.

Polyvinyl butyral: for injection molding.

Acrylonitrile, butadiene and styrene copolymer: for conventional injection molding.

14

Oil holders.

Polyethylene 1: high-grade polyethylene. Ml-6.0 for injection molding.

Polyethylene 2: high purity but lyetilea, M1-0.04 for extrusion molding.

Polyethylene 3: low density polyethylene, M1-10 for injection molding. Ultra high molecular weight ethylene: 1.000.000 average molecular weight.

Polyroinlen:, 0 for injection molding.

Block copolymer of ethylene and propylene: MS1 2.0, contains 5 wt. % ethylene, for injection molding.

Polybutene-1: for injection molding.

Poly-4-methylpentene-1: for injection molding.

Ethylene copolymer: M1-150, vinyl acetate contained 28 wt. % for injection molding. Oils.

Paraffin oil: paraffin oil with a viscosity of 10 eats (37.8 ° C).

Puftei oil: naphthenic oil 56, 98.3 ° C.

Aromatic oil: oil with aroma content, 50 wt. %, viscosity 15 eats (37 ,.

Esters: di- (C1O-oxo) sebacate.

Paraffin wax: average molecular weight 1.000.

Supplements.

Graphite: an average size of 300 mesh meshes.

Molybdenum disulfide: average particle size 300 mesh.

Teflon powder: polytetrafluoroethylene powder, medium particle size 40 mesh.

Boron nitride: an average particle size of 150 mesh.

Graphite fluoride: an average particle size of 300 mesh.

Talc: average particle size of 2 microns.

Calcium carbonate: dense calcium carbonate, average particle diameter 0.5 micron. Kaolin: average particle diameter of 1 micron.

Glass powder: average particle diameter 10 microns.

Glass beads: average particle diameter 10 microns.

Microspherical glass particles: medium particle diameter of 200 microns.

Glass fiber: diameter 10 microns, length 0.3 mm.

Carbon fiber; diameter 10 microns, length 0.5 mm.

Asbestos: class 7T.

  powder: the average particle size of the BO mesh.

In tab. 1-6 shows the proposed composition and their characteristics.

15

sixteen

Table

i pour point, pour point 137 ° C

5The value is measured at, the pour point,

6 temperature of fluidity 17, С, temperature of fluidity 138С.

17

Note and. i Pour point 258 ° С, Pour point 320 ° С, Pour point 2 ° C, 4 Molded product - soft.

18

Table 2

nineteen

20

Table 3

Note. The value is measured at 185 ° C. The melted product is soft.

ri p o d o. I w o and li c

23

24

Table 4

25

Note, i The value is measured at 185-С.

26

P r about d about l and E and with with and l and.

27

28

Table 5

29

713534

50 P II a d e l and 1 g e b a l l. five

Note, i The value is measured at.

Table 6

Prolo l with li II e

As follows from the analysis of known and proposed compositions but examples, the latter has a refined processability and the best appearance of products made from compositions.

Claims (2)

1. Patent Japopi L 21786, cl. 25N 311.1, publ. 1966. 2. Japanese patent No. 5321, cl. 53A 20, publ. 1971 (prototype).