SU759561A1 - Binder for glass plastic material - Google Patents

Description

The invention relates to a binder without a solvent for insulating plastics and structural purposes. with

Known binders based on epo-. Ksidnykh pitches which are applied to production of fiber glass plastics on working temperatures to 155 ° C. They require long-term curing at, θ high temperatures (up to 180-220 ° С) 0}.

It is also possible in the manufacture of fiberglass to use a binder containing unsaturated polyamirimide (synthesized by polycondensation of unsaturated dicarboxylic 15 acids, polyatomic alcohols and im- * aromatic or substituted and / or hydrogenated, aromatic di- or polycarboxylic acids) / monomer, radical initiator, inhibitor, accelerator curing [2].

The imides are phthalic, tetrahydrophthalic, tetrachlorophthalic, tetrabromophthalic, and endo-methyl tetrahydrophthalic, naphthalic, trimethylitic or pyromellitic acid imides.

However, the use of phthalic acid imides results in a bond-30

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These are hardening, the curing of which is inhibited by atmospheric oxygen, which causes the appearance of a cast. The use of imides with naphthalic, trimellitic and pyromellitic acid gives binders with too high viscosity. Dilution with styrene to the desired viscosity is impossible, since the compatibility of polyetherimides containing these imides with styrene is low and with increasing styrene concentration the solutions are stratified into two phases. The use of tetrachloro-and tetra-bromophthalic acid imides reduces the heat and heat resistance of the resulting binders and products based on them.

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Imides of tetrahydrophthalic and endomethylene tetrahydrophthalic acid provide technologically advanced binders that make it possible to obtain glass-reinforced plastics capable of long-term operation at 155–. 160 ° C. However, such heat resistance is insufficient for a number of applications.

The aim of the invention is to improve the heat resistance and physico-mechanical properties of fiberglass.

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The goal is achieved by the fact that the polyetherimide contains imide units of cycloaliphatic 0-dicarboxylic acids and non-halogenated epoxy resin units, and the components of the binder are used in the following ratios.%: ·

Unsaturated polyetherimide 48-60

Monomer - 35-50

Radical initiator 1-3,5

Inhibitor 0.05-0.5

Curing Accelerator 0.001-1.0

As imide units of cyclo-, aliphatic 0-dicarboxylic acids, it is preferable to use the imide units of cis- or isomethyltetrahydrophthalic acid.

As a radical initiator, it is preferable to use a mixture of tert-butyl perbenzoate and benzoyl peroxide in a ratio of 1: (0.5-1).

As an inhibitor, for example, hydroquinone, p-benzoquinone, p-tert-butylcatechol are used, and the hardening accelerator is a variable-valence metal salt, for example, naphthanate, linoleate or cobalt octoate, vanadium pentoxide.

Unsaturated polyetherimide is preformed by the polycondensation of N-hydroxylalkyl imides of cyclo-saturated melts or of unsaturated 0-dicarboxylic acids, maleic anhydride and low-molecular epoxy resins, which do not contain reactive functional groups in conditions of solidification, with the exception of double bonds (non-metallic, non-meltane), which does not contain reactive functional groups under conditions of solidification with the exception of double bonds (non-metallic, non-meltane, and they will not contain reactive functional groups in the conditions of hardening of functional groups with the exception of double bonds (anchromo nyrotephane). .. epoxy resin groups take 0.5-2.0 (0.9-1.1) mole less · and anhydride and 0.5-2 (0.9-1.1) mole Ν-hydroxyalkylamide, and · The ratio of maleic and nhydride and imide is 1: (0.9-1.1)> mostly 1: 1.

When mixed with anhydride. cycloaliphatic 0-dicarboxylic acid monoalkanolamine is slowly added (the loading order may be reversed). At the same time there is a strong exothermic effect. After the introduction of the entire amount of the second component, the temperature is raised to 160-190 ° C and cyclization is carried out, obtaining N-hydroxyalkyl imide. Maleic anhydride and catalyst are added to it at a temperature not higher than 150 ^ and heated at 120-180 ° for 0.5- 3 hours. Then an epoxy resin is added to the acidic ester obtained at this stage at 90-130 ° C and heated for 1-5 hours at 120-180 °. A polyetherimide with an acid number of not more than 30 (5-20) mg mg KOH / g, ester number> 200 and a secondary hydroxyl group content of 3-6% is obtained.

As anhydrides of dicarboxylic acids, tetrahydro-, cismethyltetrahydro-, isomethyltetrahydro-, ecdimethyleny- and methylendemethylentetrahydro-, hex-; · sagydro- and methyl hexahydrophthalic acid anhydrides are used, etc. as alkanolamines-monoethanolamine, various aminobutanol, 1, b-aminohexanol. Epoxy resins are used in the following types: dianoic with a mole of not more than 500, cycloaliphatic, epoxy novolac, triglycidyl isocyanurate.

Tertiary amines, quaternary ammonium and phosphonium salts, sulfur-containing compounds (thiuram, altax, etc.) can be used as catalysts.

The resulting polyetherimides at 100-120 ° are dissolved in a polymerization monomer containing an inhibitor, for example quinone, to prevent 'gelation during dissolution and subsequent storage of the solution. The resulting solutions are cooled and injected into them the appropriate amount of accelerator. Immediately before use, the resulting composition is activated by the addition of a free radical initiator, for example, t-butyl perbenzoate.

The composition is cured by a free radical mechanism similar to the curing of ordinary (unsaturated polyethers) by the double bonds of the monomer and the double bonds (maleate and / or fumarate) of polyether amide.

PRI me R 1. Glass fiber is impregnated with a binder having the following composition, wt.%:

Unsaturated polyetherimide 55

Styrene 40.95

Tretbutylperbenzoate 1

Benzoyl peroxide paste (50% in drutyl phthalate) 1

p-Benzoquinone 0.05

IR Accelerator - 2 (10% pp in styrene) 2

Unsaturated polyetherimide, use-; Developed as a binder, it was obtained by condensation of two moles of c-methyl 2-hydroxyethylimide cis-Methyl tetrahydrophthalic acid, two moles of maleic anhydride, and one mole of EDC low-molecular epoxy resin. It contains 40 mol.% Imide and 20 mol,% fragments of epoxy resin.

Impregnated fiberglass is pressed and cured in a continuous manner to lie 80-160 ° C for 1015 minutes.

The resulting fiberglass has the following characteristics:

Surround; electrical resistance 1.7? 10 * Om. cm at 20 ° C and 2.4: 10 ' ^g At 180 ° C, the tangent of the angle di5

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electrical losses tdb 0.006 at 20 ° C and 0.05 at 180 ° C.

Destructive bending stress 3012 kgf / cm ¹ .

Fiberglass can be operated for a long time at temperatures up to 180 ° C.

PRI mme R 2. Steklozggut impregnated with a binder having the following composition, wt.%:

Unsaturated polyetherimide 50

Styrene .42,4

Ethylene Glycol Monomethacrylate 5

Tretbutylperbenzoate 1

Benzoyl peroxide paste (50% in dibutyl phthalate) 1.5

p-Benzoquinone 0,1

NK-3 accelerator (10% solution in styrene) 1

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The unsaturated polyetherimide is obtained by 20 polycondensation of two moles. ' I-Methyl tetrahydrophthalic acid Ν-2-κ-ethyl ethyl imide, two moles of maleic anhydride and one mole of ED-22 epoxy resin. it contains _ 40 mol.% imide and 20 mol.% fragments of epoxy resin.

Impregnated glass fiber is molded and cured in a continuous way in dies at 80-160 ° C for a few minutes. The speed of 0.8-1.5 m / min. The resulting profile products are suitable for use as mortise wedges, rods, etc.

The physicomechanical and electrical properties of glass profiles are as follows:

Operating temperature, ° C 180

Breaking resistance, H 4000

Destructive stress under tension, n _p 9400

Water absorption,% 0.4

Breakdown voltage along the fibers, kVeff 23

Example 3. Glass mats are propy- 45

rolled binder of the following composition, wt.%:

Unsaturated polyetherimide 59

Styrene 34.9 50

Tretbutylperbenzoate

Benzoyl peroxide paste (50% in dibutyl phthalate)

P-Benzoquinone

NK-3 accelerator

Unsaturated polyetherimide

polycondensation of two moles of is-methyl-tetrahydrophthalic acid Ν-2-hydroxyethylimide, two moles of maleic anhydride and ONE: a mole of 2, α-dioxydiphenylpropane diglycidyl ether. The content of imide and epoxy fragments in it is 40 and 20 mol.%, Respectively.

Impregnated glass mats are stacked in 2 mm thick bags and a form - 65

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at 80–160 ° C for 10–15 min by contact molding.

Properties of the obtained fiberglass:

. Destructive stress at bending, kgf / cm ² 2800,

Surround electric

resistance, Ohm.cm, at 20 ° С 5.3: 10 *

at 180 ° С 4,3'10 ^1g

Weight loss over 30 days of aging at 220 ° C,% 2.1

The resulting fiberglass has a working temperature of 180 ° C.

Fiberglass based on the proposed polyetherimide binders can be widely used! For the preparation of a large range of products (sheets, cylinders, profiles, etc.) suitable as insulation and design materials in various sectors of the national economy.

Binder for fiberglass we combine manufacturability, low curing temperatures (80-160 ° C) and a white curing rate inherent in the above prototype, with significantly higher thermal and heat resistance, physical-mechanical and electrical properties of the finished fiberglass obtained on its basis.

Claims (3)

Claim 1. Binder for fiberglass containing unsaturated polyetherimide, monomer, radical initiator, inhibitor, curing accelerator, which is due to the fact that, in order to improve the heat resistance and physicomechanical properties of fiberglass, this polyetherimide contains imide units of cycloaliphatic '0- dicarboxylic acids and non-halogenated epoxy resin links, and the components of the binder used in the following ratios, wt.%: Unsaturated polyetherimide 48-60 Monomer 35-50 Radical initiator 1-3,5 Inhibitor 0.05-0.5 Curing Accelerator 0.001-1.0 2. Binder on π. 1, casting by the fact that, as the 'imide units of cycloaliphatic 0-dicarboxylic acids, polyetherimide contains imide units of cis- or iso-, methyltetrahydrophthalic acid. 3. Binder for PP.1 and 2, about the fact that as a hundred of the radical initiator used a mixture of tert-butylperbenerate 759561 th benzoyl peroxide in the ratio of 1: (0.5-1). ' '