RU1787161C - Compound for solid granulated molding material - Google Patents

Abstract

Usage: for products of technical and electrical purposes. The inventive composition contains (wt.%): Solid unsaturated polyester (the product of the interaction of unsaturated polyester based on maleic anhydride, aliphatic or aromatic glycol with alkaline earth metal oxides with an acid number of 10-32 μm KOH / g, the ratio of hydroxyl and carboxyl groups 1.7-5.75: 1, cations of alkaline earth metals and carboxyl groups 0.0033-0.03: 1) 13.0-25.5; diallyl phthalate oligomer 2.5-13.0; dicumyl peroxide 2.0-4.0; glass filler 20.0- 35.0; particulate filler 30.5-47.0; lubricant 1.0-2.0; pigment 1.5-2.5. The components are combined in a mixing chamber for 10 min, the mixing speed is 100 rpm, the material is crushed into granules. Mate. The rial is processed into articles by compression and injection molding. 2 tab. They are subject to such requirements as high electrical characteristics of products at room and elevated temperatures and when exposed to aggressive media, as well as good flowability and lack of caking for a long time without deterioration of recyclable ™. Such composite materials are convenient for processing by automated methods: injection molding, compression and transfer pressing, etc. using serial, non-specialized equipment. fe V | 00 h Pts

Description

In addition, such materials satisfy increased environmental requirements, since their preparation and processing are not associated with the use of highly toxic volatile substances such as styrene, FAA, etc.

A known molding composition based on unsaturated polyesters is a polycondensation product of fumaric, maleic, itaconic acids with glycols (ethylene, diethylene glycols, butanediol, glycerol). The composition contains a crosslinking agent (diallyl phthalate, triallyl cyanurate and their based polymers), a reinforcing filler, a curing initiator. vinyl polymer 1. The described composition has good formability, but does not provide sufficient chemical resistance and electrical insulating properties (specific surface resistance PS 101 Ohms, and after exposure to water drops to 10-1012 Ohms, while p $ not less than 1015 -1016 ohms).

Also known is a solid molding composition for injection and injection molding based on NPEF-A, polycondensation products of 2.2 5 5is- (4-hydroxycylhexyl) prbpan and ethylenically unsaturated dicarboxylic acid (fumaric) and NPEF-B polycondensation product al - kylenglycols, ethylenically unsaturated dicarboxylic acid and unsaturated dicarboxylic acid, a crosslinking solid monomer such as acrylamide, organic peroxide, inert filler 2. The described composition also has relatively low dielectric characteristics sticks (/% 10 Ohm, / v 1014OM CM. tg b - 0.045), which noticeably worsen after exposure to moisture, because compositions containing acrylamide derivatives are not waterproof.,

European Patent No. 0021690 (USA) 3 describes a method for preparing a curable solid composition comprising a mixture of an amorphous NPEF, a crosslinking monomer containing ethylenically unsaturated groups, a curing initiator, fillers, etc. and oxides of alkali and alkaline earth metals in amounts of 1-5% (thickening additives).

The use of the process of thickening liquid systems to obtain solid compositions is not technologically advanced. In addition, the liquid, easily volatile and toxic monomers used in the patent (styrene, C-styrene, methyl methacrylate, etc.) do not provide enhanced sanitary and hygienic characteristics of molding compositions.

currently presented by industry and do not allow to obtain sufficiently waterproof materials that retain high electrical insulating characteristics after exposure to moisture.

The closest technical solution to the invention is molding composition 4. The main components of the composition are:

A) 10-45 h NPEF with a softening temperature of 50 ° С (based on fumaric, itanoic, isoterephthalic, adipic acids and ethylene glycol, diethylene glycol and

DR.);

5 B) 1-20 hours of epoxy resin (ES) with an epoxy equivalent of 150,

0.1-10.0 h epoxy curing agent:.

0.3-10 hours crosslinking agent (oligomer

0 and diallyl phthalate monomer, styrene, methyl methacrylate, acrylamide, M-methylol acrylamide, etc.),

curing initiator (dicumyl peroxide),

5 powdered fillers (Ca-COz),

reinforcing filler - fiberglass.

lubricant (Zn stearate).

0 in this composition, acrylamide derivatives having poor water resistance are used as the crosslinking monomer. This leads to a strong deterioration in the electrical performance of the material after barely exposure to moisture (p and ps 10 ° -1010 Ohm-cm and Ohm). The granulate used does not possess storage stability (it does not crumple at 25 ° C for a week, and at t 45 ° C for three days). At the present time

0

5

preservation of the flowability of granular molding materials should be ensured for at least 12 months without deterioration of recyclable ™. Introduction to 20 wt.h. epoxy resin and its hardener plate will adversely affect the timing

material storage. Epoxy compositions are known to have a limited shelf life due to premature curing (typically not 3 months).

0 In addition, the presence of an epoxy resin with a hardener can lead to premature curing of the composition during its homogenization in a screw mixer at temperatures of 80-100 ° C.

5 The purpose of the invention is to increase the shelf life of granular flowability and to increase the electrical insulating properties that remain at a high level after exposure to an aggressive environment.

The goal is achieved in that the composition as a modified unsaturated polyester (NPEF) contains the reaction product of an unsaturated polyester with alkaline earth metal oxides, characterized by an acid number of 10-32 mgKOH / g; the ratio of OH and COOH groups (1.7-5.75) 71 and the ratio of Mei metal cations COOH is (0.0033-0.03) / 1, and as a crosslinking component, the diallyl phthalate oligmer in the following ratios of system ingredients May. %: Modified. NPEF 13.0-25.5 Oligomer of diallyl phthalate RDAF 2.5-13.0 Glass filler 20, 0-35.0 Dispersed filler 30.5-47.0 Lubricant 1.0-2.0 Pigment. 1.5-2.5 Dicumyl peroxide2, 0-4.0 As unsaturated polyesters, the polycondensation products of aliphatic and cyclic glycols (propylene glycol, hydroxypropylated diphenylol propene and tetrachloro-bromo-diane, ethylene glycol) with maleic anhydride and / or dimethyltereft are used alkaline earth metal oxides in an amount of from 0.01-0.05%, which are introduced into the NPEF melt after reaching 10-32 mgKOH / g, depending on the type of polyester, before combining it with a crosslinking oligomer. The resulting modified NPEFs are characterized by:

1) c.h. 10-32 mgKOH / g

2) the ratio of OH and COOH groups (1.7-5.75) 71

3) the ratio of Me cations to COOH (0.0033-0.03) 71

A diallyl phthalate religomer with a mp of 95-110 ° C, a polymer content of 0.5%, MP 800 (TU 6-05-241-321-87) is used as a crosslinking component.

As a reinforcing filler, glass filler () TU 6-11-506-80, glass filler BS-13-140P-4-881, etc. are used.

Dispersed fillers are traditional fillers, such as chalk, kaolin, calcite, various types of talc (TRLL, microtalc, TMK-28, etc.), etc.

Dicumyl peroxide (TU 38.40255-83) is used as a curing initiator.

In addition, the composition contains a lubricant (Ca or Zn stearates) as well as a pigment (lithopone, titanium dioxide, blue phthalocyanine pigment).

5In order to obtain a new solid granular molding composition that meets the required requirements, a new NPEF modified with alkaline earth metal oxides is used

0 in an amount of 0.01-0.05% and characterized by:

1) c.h. 10-32 mg KOH / g

2) the ratio of OH and COOH groups (1.7-5.75) 71

5 3) the ratio of metal cations and COOH groups

(0.0033-0.03) 71

New modified NPEF mixed with diallyl phthalate oligomer

0 (ODAF), curing initiator, glass filler, disperse fillers (chalk, kaolin, calcite, talc, etc.), curing initiator (dicumyl peroxide), lubricant, pigment in the mixer

5 continuously or periodically at t ° 80-100 ° C and is subjected to granulation in the plane of the forming head, or crushing into granules of 2-6 mm in size.

The obtained molding granular material is characterized by good electrical insulating properties (pv, ps.igd), which remains at a high level after exposure to chemically aggressive environments (in particular water, solutions

5 alkalis and acids). The granulate is stable during storage (12 months) without deterioration of properties and processability. In addition, the material is perfectly processed by all types of pressing and injection molding. It allows to obtain complex thin-walled products (including fittings) with good mold filling, without defects; products have a glossy surface, dimensional stability. Material

5 has improved hygiene characteristics due to the fact that volatile toxic components are completely absent.

0 It is technologically advanced when produced by continuous technology in industrial equipment: there is no likelihood of premature curing at the homogenization stage in the mixer screw, there is no sticking when cutting into granules.

The proposed material is intended for products of the electronic, electrical, automotive, radio and other industries (capacitor stators, coils).

A distinctive feature of products made from granular materials based on NPEF is good mechanical workability (grindability and polishability), which is often necessary in the industry of electronic products.

The composition has traditional performance characteristics (e.g., impact strength, bending, compression, etc.) at the level characteristic of NPEF-based granules.

The content of the components and their ratios are given in table 1, and the properties of the materials in table 2 ..

Example 1. In a four-necked flask equipped with a stirrer, an inert gas bubbler, a thermometer and a Dean and Stark trap for collecting condensation water, 1.1 mol of hydroxypropylated diphenylol propane and 1.0 mol of maleic anhydride are charged. The initial mixture is heated to t 195-200 ° C and maintained at this temperature until a polyester with k.ch. 10 mg KOH / g After that, the polyester arasplit was introduced with 0.05% MDO and was triturated at 195 ° C for I hour. The resulting oligoester is characterized by:

1) the ratio of OH and COOH groups is 5.75 / 1;

2) the ratio of metal cations (MD) to COOH is 0.0033 / 1.

The solid oligoester is combined with the diallyl fatalate oligomer (ODAF), glass filler SP-A. kaolin, dicumyl peroxide, Ca stearate and TI02 in the ratio:

Modified Polyester Diallyl Phthalate Oligomer ODAF Glass Filler SP-A Kaolin Stearate Sa Dicumyl Peroxide

in a batch mixing chamber at t 95 ± 5 ° C for 10 minutes at a mixing speed of 100 rpm. The resulting material is crushed on an Olmos crusher. The obtained granulate has good flowability, does not caking during the entire storage time (12 months), has chemical resistance and excellent electrical insulating properties. The material is perfectly processed into products by compression, transfer pressing and injection molding

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0

5

0 5

0

5

0

5

0 5

pressure, fills the mold well. Products have a glossy surface.

Example 2. The oligoester, the synthesis of which is carried out by analogy with example 1 to k.ch. 13 mg KOH / g; at the last stage, 0.03% of MgO was added and incubated for 1 h. The finished product is characterized by:

1) a ratio of OH and COOH groups of 3.78 / 1;

2) the ratio of cations Md and COOH-groups is 0.021 / 1.

The resulting oligoester is mixed with an ODAF oligomer, a glass filler, microtalc, a curing initiator, Ca stearate, and TiO2 in a continuous screw mixer in the required ratio:

Modified

NPEF25.5

Odaf2.5 diallyl phthalate oligomer

Glass filler

SP-A35

Microtalc31.5

Stearate Ca1.0

TU22.5

Dicumyl peroxide 2.0 at t 80-100 ° C and is granulated by cutting on the plane of the forming head into granules 2-4 mm in size, preserving flowability during storage for a year. The resulting granules are processed into products having good electrical insulating characteristics, water and chemical resistance.

Example 3. In a four-necked flask equipped with a stirrer, an inert gas bubbler, a thermometer and a Dean and Stark trap for collecting condensate, 0.4 mol of dimethyl terephthalate and 1.1 mol of propylene glycol and 0.02 May are charged. % (of the starting components) of the catalyst - Zn acetate. The starting mixture was heated to t 175-185 ° C and the transesterification was continued until methanol evolution ceased. The reaction mass is cooled to t 110-115 ° C and 0.6 mol of maleic anhydride is introduced, the temperature is raised to 185-195 ° C and condensation is carried out to r.h. 30 mg KOH / g Thereafter, 0.01% ZnO is introduced into the melt and maintained at a synthesis temperature of 1 hour with a working stirrer.

The finished oligoester is characterized by:

1) a ratio of OH to COOH of 1.7 / 1;

2) the ratio of cations to COOH is 0.0033 / 1.

Oligozfir is mixed with ODAF, glass filler, calcite, Ca stearate, dicumyl peroxide in a continuous screw mixer at t 80-100 ° C and granulated on granules 2-4 mm; stored for 12 months without deterioration recyclable ™.

The resulting material has chemical resistance and high electrical insulating properties:

Modified

NPEF17.7

Dialylphthalate oligomer 9, 3

Glass filler

SP-A35,0

Calcite 30.5

Stearate Ca2.0 TU2 ..- 2.5

Dicumyl Peroxide 3.0

PRI me R 4.

The synthesis of polyester is carried out according to the scheme described in example 1. The ratio of the components according to table 1. After reaching to, h. 25 mg KOH / g, 0.03% of MgO was added to the melt.

The finished polyester is characterized by:

1) the ratio of OH: COOH 5.75 / 1;

2) the ratio of MD: COOH 0,009 / 1. The oligoester is combined with the ODAF oligomer, glass filler, chalk, dicumyl peroxide, Ca stearate and lithopone in the ratio:

Modified NPEF 20.0 ODAF 8.0 Glass filler 20 Talc TRPN 47 Stearate Ca 1.0 Lithopon 2.0 Dicumyl peroxide 2.0 at a temperature of 85 ± 5 ° C in a continuous screw mixer. Granules are obtained by cutting on the plane of the forming head (granule size 3-6 mm). The material does not stick, stable during long-term storage. It has a complex of high electrical characteristics that remains after exposure to aggressive media. It is processed by injection molding and all types of pressing.

PRI me R 5, Unsaturated oligoester obtained according to the scheme described in example 1. The ratio of the components used in accordance with table 1. Synthesis lead to k.ch. 20 mg KOH / g, after which MgO in the amount of 0.02% is introduced into the melt of oligoester. The final product is characterized by:

1) the ratio of OH: COOH 5.75 / 1;

2) the ratio of MD: COOH 0,0075 / 1. In the next step, NPEF is mixed in a continuous mixer.

at t 80-100 C with an ODAF oligomer, glass filler SP-A, chalk, dicumyl peroxide, Ca stearate and TiOa and granulated by cutting on the plane of the forming 5 head into granules 2-5 mm in size. The granulate retains flowability without impairing processability. It has high electrical insulation characteristics that persist after exposure to arpec-v 0 active media:

Modified NPEF15.0 Oligomer ODAF. 13.0 Glass Filler

5 SP-A20.0 Mel 47.0 Stearate Ca 1.0 TiO2 2.0 Dicumyl peroxide 2.0 0 Example 6. The unsaturated polyester is synthesized according to the scheme described in Example 1. Then, 0.05% MDO is introduced into the melt and maintained at t 195 ° C for 1 hour. The resulting polyester is characterized by: 5 1) a ratio of OH and COOH groups of 5.75 / 1;

2) the ratio of metal cations (MD) to COOH is 0.0033 / 1.

Solid oligosfire is combined with oligomer 0 of diallyl phthalate (ODAF), glass filler SP-A, chalk, dicumyl peroxide, lithopone and paraffin in combination:

Modified

5 oligoester 15.0 Oligomer diallylphthal ata ODAF 13.0 Glass filler SP-A 20.0 0 Mel 47.0 Lithopone 2.0 n-Eicosan (paraffin) 1.0 Dicumyl peroxide 2.0. in a continuous mixer at 5 t, 80-100 ° C and granulated by cutting on a plane of the forming head into granules 2-5 mm in size. The granulate retains flowability for 12 months without deterioration of processability. It has high 0 electrical insulating characteristics that remain after exposure to aggressive media.

Example 7. An unsaturated oligoester is prepared according to the scheme described in Example 1, 5, after which 0.02% of MgO is introduced into the melt. The final product is characterized by:

1) the ratio of OHtCOOH - 5.75 / 1;

2) the ratio of MD: COOH - 0,0075 / 1,

Next, NPEF is mixed in a mixer.

continuous operation at t 80-100 ° С

ODAF oligomer. fiberglass, aluminum hydroxide, chalk, dicumyl peroxide, pigment and 2p stearate and is granulated on the plane of the forming head into granules of 2-5 mm. The material has high electrical insulation properties and maintains flowability without deterioration. The recyclable ™ is 12 months old. Modified Polyester 17.7 Oligomer diallyl. phthalate (ODAF) 9.3 Fiberglass

BS-13-140R-4-88-120.0 A1 (OH) s 30.0 Chalk: 17 CreapaTZn 1.5. Dicumyl peroxide 3.0 Phthalocyanine blue pigment 1.5 Example 8. An unsaturated oligoester is prepared as in Example 6. Next, the NPEF is mixed in a continuous mixer with an ODAF oligomer, glass filler, chalk, Ca stearate, dicumyl peroxide and TIO2 in the following ratio:. Modified oligoester 17.7 ODPA diallyl phthalate oligomer 9.3 Glass filler SP-A 26.0 Mel .. 41.85 Stearate Ca 2.0 Dicumyl peroxide 3.00 T102 0.15. PRI me R 9. Into the oligoester, the synthesis of which is carried out by analogy with example 1 to CKH 12 mg KOH / g, at the last stage, 0.025% MdO is introduced and kept for 1 hour. The finished product is characterized by

1) by the ratio of OH and COOH groups: 3.75 / 1 ;:

2) the ratio of cations Md and COOH-groups is 0.03 / 1.

The resulting product is mixed with an ODAF oligomer, glass filler, chalk, aluminum hydroxide, dicumyl peroxide, pigment and Ca stearate in a continuous mixer at t 80-100 ° C and then granulated on the plane of the forming head into granules for 2-5 minutes. The material has high electrical insulation properties and maintains flowability without deterioration. The recyclable ™ is 12 months old.

Modified

polyester 17.7

Diallyl phthalate oligomer (ODAF) 9.3 Glass filler BS-13-140P-4-88-1 20.0 A (OH) s 30.0 Chalk 17.0 Stearate 1.5 Diculim peroxide 3J) Blue phthalocyanine pigment 1, 5

Example 10 (comparative). Synthesis

oligoester lead according to the scheme described in

Example 1, to an acid value of 10 mg KOH / g.

In the last step of the synthesis,

0.005% MdO.

The resulting NPEF is characterized by the following characteristics:

1) the ratio of OH and COOH groups is 5.75 / 1;

2) the ratio of cations Md to COOH groups 0.00033.

The oligoester is combined with the ODAF oligomer, glass filler SP-A, kaolin, dicumyl peroxide, Ca stearate in the ratio:

Modified NPEF .20 Oligomer diallylphthalate ODAF. 8 Glass filler

SP-A25 Kaolin 41.5 StearateSa 2.0 Dicumyl Peroxide 2

at t 85 5 ° C in a continuous mixing chamber and granulated by cutting on the plane of the forming head. The properties of the obtained material are given in table 2,

 PRI me R 1.1 (comparative). Synthesize the oligoester according to the scheme described in example 3, to k.ch. 40 mg KOH / g, after which 0.05% of MgO was introduced into the melt. The resulting oligomer is characterized by:

1) the ratio of CH - and COOH-groups of 1.6 / 1;

2) the ratio of cations Md and COOH-groups of 0.05 / 1.

The finished product is a sticky, low melting mass. When mixed in a batch mixer with an ODAF oligomer, a glass filler, talc TMK-28, Ca stearate, TiOa and peroxide, dicumyl s of the following ratios:

Modified

NPEF20.0

Oligomer ODAF 8.0

Glass filler Talc TMK-28 Stearate Sa

TIQ2

Dicumyl Peroxide

The resulting material is a highly viscous, sticky mass that cannot be crushed,

PRI me R 12 (comparative). Unsaturated oligoester obtained according to the scheme described in example 1. The synthesis is carried out to k.h. 5 kg KOH / g, after chegre 0.01% ZnO is added.

The product is characterized by:

1) the ratio of OH: COOH 5.87 / 1;

2) a ratio of ZmCOOH of 0.015 / 1.

The resulting oligoester is a high melting and high molecular weight product (ton 120 ° C). Obtaining a composite material by combining the synthesized oligoester in a melt with a crosslinking component of ODAF, glass filler, and other components of the system is impossible due to premature curing of the composition at such temperatures directly in the mixer.

Claims (1)

Claims A composition for a solid granular molding material comprising a solid unsaturated polyester, 20 diallyl phthalate oligomer, Diku peroxide 47 mils, Glass filler, dispersed filler 1.0, lubricant and pigment, distinguish 2.0. As a result of the fact that, in order to improve the electrical 2.0 insulation properties, increase their stability in the aquatic environment and increase the shelf life of granules, it contains, as a solid unsaturated polyester, the product of the interaction of unsaturated maleate-based polyester 10 - new anhydride and aliphatic or aromatic glycols with alkaline earth metal oxides, with an acid number of 10-32 mg KOH / g, the ratio of hydroxyl 15 and carboxyl groups (1.7-5.75): 1., alkaline earth metal cations and carboxyl groups (0.0033 -0.03): 1 in the following ratio of the components of the composition, wt.%: 20 solid unsaturated polyester 13.0-25.5; diallyl phthalate oligomer 2.5-13.0; dicumyl peroxide 2.0-4.0; 25 Glass filler 20.0-35.0. dispersed filler 30.5-47.0: lubricant 1.0-2.0; pigment 1.5-2.5. thirty The compositions used modified NPEF Table 1 The main akepluetacioin characteristics of the composition Continuation of table 1 table 2 Continuation of Table 2