Method of manufacturing sheet organic glass for neutral light filters


FIELD: polymer materials.

SUBSTANCE: sheet organic glass is obtained by way of bulk (co)polymerization of (meth)acrylic acid esters in presence of UV absorber, radical polymerization initiator, and light-absorbing additive. Process involves monomer prepolymerization and subsequent final polymerization if mixture in flat-parallel mold. Methacrylic acid esters utilized are, in particular, methyl methacrylate or its mixtures with (meth)acrylic acid or (meth)acrylic acid esters. Light-absorbing additive is methane decomposition product obtained in high-voltage discharge plasma at atmospheric pressure and characterized by loose density 0.65-0.85 g/cm3 and specific pore volume 0.40-0.50 cm/cm3. Additive, taken in amount 0.001-0.01 wt parts per 100 wt parts monomer, is mixed with prepolymer. Resulting mixture is affected by ultrasound and then polymerized in mold until conversion is completed. Sheets manufactured according to invention are suitable for neutral light filters employed in instrumentation engineering, in personal protection devices, and in sporting airplane glazing operations.

EFFECT: improved optical characteristics of glass due to more uniform light transmission in visible spectrum region.

1 tbl, 15 ex

 

The invention relates to the field of production of organic glass sheet (co)polymerization in the weight of esters of (meth)acrylic acid used for the manufacture of neutral filters that are used in industry (manufacturing of monitors), personal protection (glazing protective helmets for pilots) and glazing sport aircraft.

Organic glass nd filters must absorb ultraviolet radiation in the wavelength 220-340 nm (transmittance of 0%) and in the visible region of the spectrum (400-750 nm) having a transmittance in the range of 10-80% depending on its purpose. For a perfect neutral color organic glass must also have the same transmittance in the whole range of the visible spectrum, since the dependence of transmittance on wavelength in the visible part of the spectrum reduces visibility in low-light conditions, affects the range of object recognition when using such filters as, for example, glass cab sport aircraft.

A method of obtaining organic glass for optical filters, in which dissolve the fat-soluble dye pure blue antrahinonovye in the number 0,008-of 0.025 parts by weight per 100 parts by weight of methyl methacrylate (MMA) or green antrahinonovye the 2ZH in the number 0,0085-0,095 parts by weight of in MMA, after the dissolution enter the initiator, academicresources acid, and additives: UV-absorber (fenilsalitsilat) and stearic acid, then hold terpolymerization mixture to 3-4% (expiry 3-8) and then polimerizuet in ploskoparallyel form a thickness of 2-6 mm Receive filter blue or green in color, used in medicine for protective eyewear. (One-time process regulation No. 2-90 to receive organic glass and polymeric materials, GUP "Institute of polymers", 1990). The main disadvantage of this filter is a certain dependence of transmittance on wavelength in the visible spectrum, which does not allow to consider them as perfectly neutral density filters, so that the plexiglass is the ratio of the integral transmittance (To) 55%, when the wavelength of λ=400 nm, the transmittance is 40%, and at λ=750 nm 62%,i.e. ΔK=22%.

Also known is a method of obtaining optical filter to protect vision by pre-dissolving 0,0061-0,0063 parts by weight of paste suhovaltsovannyh based on chlorinated polyvinyl chloride (PVC) and carbon black 100 parts by weight of MMA within 60 min at a temperature of 30-35°With subsequent mixing the resulting solution with of 0.00006-0,00008 parts by weight of the fat-soluble dye pure blue antrahinonovye, 0.2 to 0.5 parts by weight of fenilsalitsilata and azonitrile the m somaclonal acid. Everything is stirred for 40 minutes at 35-40°With, then at a temperature of 65 - 70 °conduct terpolymerization mixture to conversion of 3-4%. The resulting prepolymer is poured in the form of two plane-parallel polished silicate glasses 500x500 mm, strip them of a polyvinyl chloride tube. Get plexiglass thickness of 2.5-3.5 mm (patent RF №2015140, C 08 F 120/14, publ. 30.06.94 g). The transmittance of the glass varies from 48-68% at a wavelength of 400 mm, up to 64-72% at 700 mm, i.e. Δequal To 14-16%. Thus, the above-described neutral density filters do not have a uniform transmittance in the visible spectrum, which limits their use.

The technical result of the invention is to improve optical characteristics of the sheet of plexiglass for the neutral light filters through achieving a more uniform light transmission of the glass in the visible part of the spectrum.

To achieve the technical result in the production method of organic glass sheet for the neutral light filters through (co)polymerization in mass of esters of methacrylic acid in the presence of a radical polymerization initiator, a UV absorber and a light absorbing additives, including terpolymerization monomer and subsequent depolymerization mixture in the plane-parallel form, serves as the Fira methacrylic acid to use methyl methacrylate or a mixture of methyl methacrylate and (meth)acrylic acid or its esters, and as a light-absorbing additives to use the product decomposition of methane in the plasma of the high-voltage discharge in atmospheric pressure with a bulk density of 0.65-0.85 grams/cm3and the specific pore volume 0,40-0,50 cm3/g in the amount of 0.001 to 0.01 to 100 parts by weight of monomer, which is mixed with the previously obtained prepolymer, to act on the resulting mixture ultrasound and then polimerizuet it in plane-parallel form to complete the conversion.

Light-absorbing additive is a product of the decomposition of methane in the plasma of the high-voltage discharge in atmospheric pressure with a bulk density of 0.65-0.85 grams/cm3and the specific pore volume 0,40-0,50 cm3/g obtained at the Scientific and production private unitary enterprise "technologies of chemical physics", Minsk, Technological regulation No. 1.05-03 to receive carbon composition for use as a filler in obtaining organic glass.

The above product is composed of amorphous carbon (not less than 50%), carbon nanofibers with a diameter of 100-200 nm, a length of 1-1 .5 μm and multiwall carbon nanotubes with a diameter of 20-40 nm, length of 1-10 μm.

As esters of methacrylic acid using methyl methacrylate (MMA) or a mixture of MMA (meth)acrylic acid, butyl acrylate, dimethacrylate of ethylene glycol, with cyclohexylmethanol, with fenilsalicilat is m, with isobutylacetate etc.

As an initiator of radical polymerization, the proposed method can be used azo-bis-(isobutyronitrile), dicyclohexylperoxydicarbonate, benzoyl peroxide, peroxide Laurila and other

As the UV absorber can be used fenilsalitsilat, Tinuvin P and others.

Below are specific examples of implementation of the claimed method of producing a sheet of plexiglass for nd filters.

EXAMPLE 1

of 0.01 parts by weight of the product of decomposition of methane in the plasma of the high-voltage discharge in atmospheric pressure with a bulk density of 0.65-0.85 grams/cm3and the specific pore volume 0,40-0,50 cm3/g is mixed with 100 parts by weight of the prepolymer of methyl methacrylate. A prepolymer is prepared as follows: methyl methacrylate (MMA) in the presence of 0.03 parts by weight of azo-bis-(isobutyronitrile)(ADN) is polymerized in a water bath at a temperature of 70-80°and With stirring until the viscosity of 85 cSt (conversion 3-5%).

The mixture is subjected to ultrasound frequency 44 kHz on the device UZDN-2T for 25 minutes. Then to the mixture is added to 0.05 parts by weight of Tinuvin P (UV absorber) and 0.06 parts by weight of azo-bis-(isobutyronitrile), the mixture is poured in the form of silicate glasses and cushioning tube and polymerized in air Cabinet according to the following mode:

Stage 1: 45° - 6 hours;

2nd stage:

60° With - 0.5 hours;

80° - 0.5 hours;

100° - 0.5 hours;

120° - 1.0 hours.

The obtained organic glass size (HH) mm has a uniform gray color. The transmittance of the glass at 400-750 nm was determined on a spectrophotometer SF-18, at 220-340 nm on the spectrophotometer SF-26. The integral transmittance was determined according to GOST 15875-80. The obtained data are given in the table.

EXAMPLES 2-10

Method for producing organic glass and methods of test as in example 1. The number of light-absorbing additives, the composition of the Monomeric mixture and optical properties of organic glass shown in the table.

EXAMPLE 11

of 0.004 parts by weight of light-absorbing additives (carbon composition) is mixed with 85 parts by weight of the prepolymer of MMA. A prepolymer is prepared as follows: methyl methacrylate in the presence of 0.03 parts by weight of azo-bis-(isobutyronitrile) (ADN) is polymerized in a water bath at a temperature of 70-80°and With stirring until the viscosity of 85 cSt (conversion 3-5%). The mixture is subjected to ultrasound frequency 44 kHz on the device UZDN-2T for 25 minutes. Then to the mixture is added to 0.05 parts by weight of Tinuvin P (UV absorber) and 0.02 parts by weight of azo-bis-(isobutyronitrile) and 15 parts by weight of methacrylic acid (MAC), the mixture is poured in the form of silicate glasses and polymerized in air Cabinet according to the following mode:

Stage 1: 45° With 6 hours;

2nd stage:

60° - 0.5 hours;

80° - 0.5 hours;

100° - 0.5 hours;

120° - 1.0 hours.

The obtained organic glass size (HH) mm has a uniform gray color. Test methods glass in example 1. Properties listed in the table.

EXAMPLE 12

of 0.002 parts by weight of light-absorbing additives (carbon composition) mixed with 95 parts by weight of the prepolymer of MMA. A prepolymer is prepared as follows: methyl methacrylate in the presence of 0.03 parts by weight of azo-bis-(isobutyronitrile) (ADN) is polymerized in a water bath at a temperature of 70-80°and With stirring until the viscosity of 85 cSt (conversion 3-5%). The mixture is subjected to ultrasound frequency 44 kHz on the device UZDN-2T for 25 minutes. Then to the mixture is added to 0.05 parts by weight of Tinuvin P (UV absorber) and 0.06 parts by weight of azo-bis-(isobutyronitrile) and 5 parts by weight of ethylene glycol dimethacrylate (DMAG), the mixture is poured in the form of silicate glasses and polymerized in air Cabinet according to the following mode:

Stage 1: 45° - 6 hours;

2nd stage:

60° - 0.5 hours;

80° - 0.5 hours;

100° - 0.5 hours;

120° - 0.5 hours;

135° - 1.0 hours.

The obtained organic glass size (HH) mm has a uniform gray color. Test methods glass in example 1. Properties listed in the table.

EXAMPLE 13 (prototype)

EXAMPLES 14-15

SPO is about getting the glass and methods of test - as in example 1. The number of light-absorbing additives and optical properties of organic glass shown in the table.

The offered method of obtaining organic glass sheet, in which the light-absorbing additives used in the product decomposition of methane in the plasma of the high-voltage discharge in atmospheric pressure with a bulk density of from 0.65 to 0.85 g/cm3with a specific volume of pores of from 0.40 to 0.50 cm3/g in the amount of from 0.01 to 0.001 parts by weight per 100 parts by weight of monomer, which is mixed with the previously obtained prepolymer, the resulting mixture is subjected to the influence of ultrasound and then polimerizuet it to full conversion, allows to obtain permanent organic glass sheet for an ideal neutral density filter having more uniform in comparison with the prototype of the transmittance in the visible part of the spectrum (2-7% vs. 14-16% on prototype) and complete absorption of ultraviolet radiation (0%transmittance at 220-340 nm). And this leads to a significant improvement of the optical characteristics of the glass, because it improves visibility in low-light conditions and distance of object recognition.

Using the product decomposition of methane in quantities less inventive, not attached to the glass Sitophilus properties (see example No. 14), and more reduces light is propuskanie glass in the visible part of the spectrum up to 4-7% (see example No. 15), which makes it impossible to use as a filter due to poor visibility.

Unlike the prototype product of the decomposition of methane is not injected into the monomer, and in a pre-obtained prepolymer in order to achieve a more uniform distribution, due to lower deposition rate of the product in the viscous medium.

The impact of ultrasound on the mixture of prepolymer and product decomposition of methane is necessary for the destruction of large particles of light-absorbing additives, which also ensures the uniform distribution.

The proposed method of producing a sheet of plexiglass for nd filters differs from prototype signs above. This allows to make a conclusion on compliance with such conditions of patentability as "novelty".

In the study of the prior art revealed that the product of the decomposition of methane in the plasma of the high-voltage discharge in atmospheric pressure with a bulk density of 0.65-0.85 grams/cm3and pore volume 0,40-0,50 cm3/g as a light-absorbing additive in obtaining organic glass is used for the first time, and, therefore, the effect of this additive in combination with other features of the proposed method on the uniformity of light transmission in the visible part of the spectrum not obvious from the prior art. This govorite compliance of the proposed method inventive step.

A method of obtaining a sheet of plexiglass for the neutral light filters through (co)polymerization in mass of esters of methacrylic acid in the presence of a UV absorber, a radical polymerization initiator and a light-absorbing additives, including terpolymerization monomer and subsequent copolymerization mixture in the plane-parallel form, characterized in that esters of methacrylic acid using methyl methacrylate or a mixture of methyl methacrylate and (meth)acrylic acid or their esters, and as a light-absorbing additives used in the product decomposition of methane in the plasma of the high-voltage discharge in atmospheric pressure with a bulk density of 0.65-0.85 grams/cm3and the specific pore volume 0,40-0,50 cm/cm3in the amount of 0.001 to 0.01 parts by weight per 100 parts by weight of monomer, which is mixed with the previously obtained prepolymer, affect the resulting mixture ultrasound and then polimerizuet it in plane-parallel form to complete the conversion.



 

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