Composition for manufacturing organic glass

FIELD: polymer materials.

SUBSTANCE: invention relates to manufacturing sheet organic glass based on methyl methacrylate copolymers and used, in particular, in making glass parts of aircrafts. Starting composition comprises per 100 wt parts of methyl methacrylate/methacrylic acid monomer mixture with 0.05-3.0 wt parts methacrylic acid, following ingredients, wt parts: phenol-type antioxidant 0.01-1.0, organic hydroperoxide 0.05-3.0, substituted thiourea 0.03-1.0, and optionally UV stabilizer 0.1-2.0, and/or UV absorber 0.005-0.5, and/or multifunctional (meth)acrylic ester as crosslinking agent 0.1-15.

EFFECT: increased heat resistance of organic glass up to ability to resist for a short time (up to 1h) heating at temperatures up to 240°C without appearance of visible defects such as bubbles and cracks.

4 cl, 1 tbl, 23 ex

 

The invention relates to the production of organic glass sheet on the basis of copolymers of methyl methacrylate used in particular for details of glazing aircraft.

In conditions of organic glass as part of the aviation glazing is exposed to one-sided aerodynamic heating when temperatures often exceed the value of its softening temperature. Therefore, one of the basic requirements for organic glass, used as an aviation glazing, high thermal stability, i.e. no visible material defects (bubbles, cracks, intense coloration, etc. under the influence of high temperatures that would impair visibility through the glazing.

Known organic glass marks the CO-120A, designed to receive parts of aircraft glazing (GOST 10667-90). Composition to obtain this organic glass includes 100 parts by weight of methyl methacrylate (MMA), peroxide initiator, 0.2 to 0.4 parts by weight of fenilsalitsilata and 0.15 to 0.5 parts by weight of stearic acid (One-time process regulation No. 4-98 to receive organic glass and polymeric materials, Federal state unitary enterprise "Institute of polymers"). Softening temperature (Tpglass CO-120A ˜120°C, thermal stability, determined by the appearance of visible defects in the stack is e, not above 190°C, the transmittance 90-92 %.

Known composition to obtain a sheet of plexiglass containing methacrylic acid is 0.1-15 wt.%, fenilsalitsilat 0.2 wt.%, azonitrile somaclonal acid 0.005 to 0.1 wt.% and MMA - the rest (RF patent 2073609, C 08 L 33/12, publ. 20.02.97). thermostability of this glass does not exceed 210°C.

Also known composition for sheet organic glass containing a mixture of 44-76 wt. % MMA, 14-16 wt. % methacrylic acid, 10-40 wt. % isobutylacetate, salol (fenilsalitsilat, UV absorber) and diphenyl (UV stabilizer), which polymerizes in the presence of a radical initiator - dicyclohexylperoxydicarbonate. The softening temperature of the glass 140-158°C, thermal stability 200-210°With (patent USSR No. 1776263, C 08 F 220/14, publ. 15.11.92).

To improve thermal stability of organic glasses in the composition to obtain impose cross-linking agents. In the latter apply poly(meth)acrylic esters of polyhydric alcohols.

Known composition for organic glass aviation, containing at least 97.5 mol % monofunctional vinyl monomer in which at least 70% of MMA and 0.4 to 2.5 mol % dimethacrylate ether of neopentyl glycol (U.S. Patent No. 4622377, C 08 F 020/20, publ. 21.01.86 year). The softening temperature of these glasses is about 120°who, thermostability 200°C.

So, also known composition of the polymerizable composition to obtain a clear organic glass for aviation, containing 100 weight. including MMA, 0.1 to 2.0 weight. hours of methacrylic acid, 0.1 to 15 weight. including glycidylmethacrylate, ˜0.1 weight. including initiator, such as peroxide of Laurila, and 0.05 weight. PM dilauryl of thiodipropionate. Education in this glass mesh patterns resulting from the interaction of parts of methacrylic acid and glycidylmethacrylate at elevated temperatures increases thermal stability of the glass by about 10 % and 200° (U.S. patent No. 5993951, 32 In 9/00, publ. 30.11.99).

The more significant the effect of increasing thermal stability of the glass is observed when used as crosslinking agents are polyfunctional acrylic esters. Known organic glass for glazing aircraft on the basis of a copolymer of MMA with polyacrylic esters (up to 5 wt. %). thermostability of this glass 210-220°C. Addition of MMA and polyacrylic esters glass contains UV absorber, preferably derived benzotriazole, UV stabilizer type space-constrained amine (both in amounts of 0.05-0.5 wt.%). Additionally may contain other monomers in an amount of 0.1-1 wt.% to regulate adhesion to the shape of the silicate glass. Initiation of polymerization is 2-which I initiated: uzasadnienie (2,2'-azo-bis-isobutyronitrile) and high temperature peroxide (tert-butylperbenzoate) (patent RF № 2163215, C 08 F 220/14, publ. 20.02.2001,).

Closest to the proposed invention is a composition for organic glass for the aviation industry, containing 60-85 wt. % of methyl methacrylate, 15-40 wt. % methacrylic acid, the radical polymerization initiator, such as dicyclohexylperoxydicarbonate in an amount of 0.01 wt. % 1·10-3-1·10-2moles per 1 mole of methacrylic acid compounds of the formula (C6H5)3MN or l4where M is Si, Ge. Organic glass on the basis of this composition has a transmittance of 91-92 %, the softening temperature of 142-164°and thermostability 230° (copyright certificate №1668369, C 08 F 220/14, publ. 07.08.91 - prototype).

The level reached thermal stability of organic glasses on the basis of the above compositions and the prototype is not sufficient, since in the short-term effects of aerodynamic heating during flight with speed up to 2.6-3 M, the surface temperature of the glazing can reach 240°C.

The aim of the invention is to improve thermal stability of organic glass to the ability to withstand short-term (up to 1 hour) heating at temperatures up to 240°without the visible defects such as bubbles, cracks, etc.

To achieve this objective, it is suggested composition for organic the ski glass, including a monomer mixture of methyl methacrylate with methacrylic acid and a polymerization initiator, which differs in that it includes a Monomeric mixture containing methacrylic acid, and 0.5-30 parts by weight, further comprises an antioxidant phenolic type, and as a polymerization initiator, an organic hydropeaking in combination with a substituted thiourea in the following ratio of components, parts by weight:

monomer mixture of methyl methacrylate and
methacrylic acid100
antioxidant phenolic type0,01-1,0
organic Gidropress0,05-3,0
substituted thioureaof 0.03 to 1.0

As an antioxidant phenolic type composition may contain diphenylolpropane (Suite), p-methoxyphenol, p-tertbutylphenol etc.

As organic gidroperekisi composition contains Gidropress hydroperoxide (CHP), parentalgalleries, Gidropress tertbutyl etc.

As the substituted thiourea, you can use tetramethylrhodamine (TMTM), atlantiscasino, definitionaudio etc.

The inventive composition for the preparation of organic glass can optionally contain:

- UV-stabilization of the EOS in the amount of 0.1-2.0 wt. 'clock on 100 parts by weight of a Monomeric mixture;

UV-absorber in the amount of 0.005-0.5 wt. h on 100 parts by weight of a Monomeric mixture;

- crosslinking agent is a polyfunctional (meth)acrylic ester in an amount of 0.1-15 wt. 'clock on 100 parts by weight of monomer mixture.

The inventive composition may also optionally contain a mixture of the above components.

As the UV stabilizer can be used diphenyl or similar aromatic compounds.

As the UV absorber can be used fenilsalitsilat, derived benzotriazole, in particular 2- (2H-benzotriazol-2-yl)-p-cresol (tinuvin P), etc.

As a cross-linking agent can be used di(meth)acrylic esters of glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, 1,4-butanediol, 1,6-hexandiol, diphenylolpropane, etc., tri - and Tetra(meth)acrylic esters of trimethylolpropane, pentaerythritol, etc.

The examples below and the table illustrates the invention.

EXAMPLE 1

In the form of siliconorganic silicate glasses size (300×300) mm 6 mm thick with a gap between them 7.2 mm pour the mixture of monomers consisting of 85 parts by weight of MMA, 15 parts by weight of methacrylic acid, and 0.5 parts by weight of diphenylolpropane, and 0.2 parts by weight of gidroperekisi cumene and 0.06 parts by weight of tetramethylrhodamine. A closed shape is placed in a water bath with a temperature of 20°C. After 15 hours the form p is meshaut in an air thermostat, heat it to 140°C for 4 hours, then maintained at 140°1 hour, cooled to 40°C for 2 hours. Then the form open and get a sheet of transparent organic glass thickness of 6 mm, melting point 138°C, the transmittance of 91.5 %. During heating of the glass sample in an air thermostat at 240°C for 1 hour it does not observe the formation of visible defects.

Thermostability was assessed by the absence of visible glass defects at step heating in the temperature range 190-240°aged 1 hour at each temperature ranging from 190°With an interval of 10°C.

The softening temperature (Tp) and transmission coefficient (KCR) the organic glass is determined in accordance with GOST 10667-90.

Properties of organic glass shown in the table.

EXAMPLE 2-14

The composition of the polymerization mixture to obtain an organic glass and its properties are given in table. The method of producing glass and test methods of example 1.

EXAMPLE 15-23 for comparison.

From the table it follows that the goal of improving thermal stability of organic glass to 240° - is achieved when ispolzovaniya obtain organic glass of the proposed structure, containing 100 wt. including the monomer mixture of methyl methacrylate and methacrylic acid with a content of methacrylic acid, and 0.5-30 parts by weight, from 0.01 to 1.0 parts by weight of phenolic antioxidant of the type of 0.05 to 3.0 parts by weight of organic gidroperekisi and 0.03 to 1.0 parts by weight of a substituted thiourea (cm/ examples No. 1-14).

The claimed composition for organic glass in comparison with the prototype has distinguishing characteristics: the specific composition of the monomer mixture, the content of antioxidant phenolic type, and use as an initiator of polymerization of organic gidroperekisi in combination with a substituted thiourea. This allows to conclude that the novelty of the claimed composition as a new essential features of the claimed composition for organic glass.

The phenolic antioxidants of the type known as stabilizers of polymeric materials [Ifought. Stabilization of synthetic polymers against the effects of light and heat. "Chemistry", LO, 1972, page 163]. However, they are also effective inhibitors of free-radical polymerization, so their introduction at the stage of obtaining organic glass in the desired concentration (≥ of 0.01 parts by weight) in the composition of the polymerization mixture at the initiation of the (co)polymerization of methyl methacrylate peroxide or azo compounds was not possible (see examples 20-2).

The use of phenolic antioxidants as inhibitors of methyl methacrylate is limited to concentrations of the order of 10-3-10-4% (GOST 20370-74, ether methyl methacrylic acid), in which they may not be stabilizers thermo-oxidative degradation. Increasing thermal stability of organic glass with the introduction of antioxidants of phenol type at the stage of polymerization has become possible only when applied in combination with a redox initiator system containing 0.05 to 0.3 parts by weight of organic gidroperekisi and 0.03 to 1.0 parts by weight of a substituted thiourea.

The use of antioxidants of another type, for example an amine, it is also impossible for initiating peroxide or azo compounds, as they are also strong inhibitors, in addition, they are able to interact with the peroxide and getoperationname components of the initiating system.

1. The composition for organic glass comprising monomer mixture of methyl methacrylate with methacrylic acid and a polymerization initiator, characterized in that it comprises Monomeric mixture in which the content of methacrylic acid, and 0.5-30 parts by weight, further comprises an antioxidant phenolic type, and as a polymerization initiator, an organic hydropeaking in combination with substituted tiomochevinoi presleduyumie ratio of components composition parts by weight of:

Monomeric mixture
methyl methacrylate and
methacrylic acid100
antioxidant phenolic type0,01-1,0
organic Gidropress0,05-3,0
substituted thioureaof 0.03 to 1.0

2. The composition according to claim 1, characterized in that it further comprises a UV stabilizer in an amount of 0.1 to 2.0 parts by weight per 100 parts by weight of monomer mixture.

3. The composition according to claim 1 or 2, characterized in that it additionally contains a UV absorber in an amount of 0.005 to 0.5 parts by weight per 100 parts by weight of monomer mixture.

4. The composition according to any one of claims 1 to 3, characterized in that it further contains a crosslinking agent is a polyfunctional (meth)acrylic ester in an amount of 0.1-15 parts by weight per 100 parts by weight of monomer mixture.



 

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