Vibration-absorbing resin and its preparation

 

(57) Abstract:

The invention relates to the field of production and application of vibration damping compositions for coatings, in particular for in-situ coating of marine areas. Mastic consists of an aqueous polymer dispersion based on vinyl acetate (with a dry residue of 40-60 wt.%), plasticizer, nepheline flame retardant, chalk, a filler with a scaly shape of the particles (crystalline graphite or vermiculite) and advanced tetramethylthiuramdisulphide. Due to the introduction of vibration in mastic of tetramethylthiuramdisuphide increases the stability of the technological properties of mastic in time (within 12 months stored technological properties). The method of obtaining the vibration mastic includes plasticization of an aqueous polymer dispersion based on vinyl acetate plasticizer and subsequent introduction to it under continuous stirring consistently chalk, nepheline flame retardant and tetramethylthiuramdisuphide, followed by homogenization of the resulting composition for at least 30 min, and then injected the filler flaky particle shape and continue mixing the components to obtain a homogeneous mass with a ratio of the blend components is propoposals compositions for coatings in particular for in-situ coating areas of the vessel.

Known [USSR Author's certificate 1451150, MKI4C 09 D 3/74, publ. 15.01.89] vibration-absorbing resin, comprising (wt.%) 45,550,0 aqueous polyvinyl acetate dispersion (PVAD), plasticized with dibutyl phthalate (DBP), 14,018,0 nepheline flame retardant (ON) and 36,040,0 filler flaky particle shape - crystalline graphite (KG).

Coating of mastic have valuable operational characteristics: high, stable in time (for three years, the ratio of the mechanical loss is reduced by no more than 812%) vibroacoustic parameters, good adhesive properties, low Flammability (index flame spread is 9.2).

The disadvantage of mastic is the instability of the technological properties of the mastic: after 35 days from the date of manufacture mastic begins to noticeably lose their mobility, and after one month storage, the value of this indicator falls approximately three times. Negative consequences of gelled mastic are:

the difficulty unloading mastic from storage containers (cans, drums), as thick mastic impossible zastavki mastic after storage for use as unloaded crumb mastic almost unable to turn into a homogeneous paste, which is freshly prepared mastic;

inhomogeneous mastic bad is applied to temperame surface;

lower (2530%) vibroacoustic damping performance coatings mastic stored in one month than coatings formed from freshly prepared material.

Described vibration-absorbing resin obtained by sequential injection at room temperature and under continuous stirring in PVAD plasticizer - DBP, and filler flaky particle shape - KG when the above ratio of the blend components [USSR Author's certificate 1451150].

However, this method cannot provide mastic stable over time technological properties.

Also known [RF Patent 2035482, MKI6C 09 D 131/04, publ. 20.05.95] vibration-absorbing resin, comprising (wt.%) 39,456,0 water plasticized PVAD, (dry residue 4060 wt.%), 11,819,0 ON, 26,042,0 KG, 2,28,0 chalk (M) and 0,54,6 of alkylbenzyldimethylammonium (ABP). As a plasticizer mastic contains DBP or triacetate of glycerol (TAG).

Produces the C it within a specified period of time damping coatings are characterized by a complex of high values vibroacoustic, adhesive and fire performance.

However, the increase of storage period of vibration of the postmark of the composition, more than one month accompanied by a decrease in the mobility of mastic, its zagustevanii and associated above-described negative consequences (difficulty unloading mastic from the storage tanks, the need for extensive and intensive mixing of mastic after storage for preparation to use, the reduction of vibroacoustic damping performance coatings in 2530%).

Specified mastic is obtained by successive addition at room temperature and under continuous stirring in PVAD plasticizer (DBP or TAG), with scaly filler particle shape - KG, M and ABP when the above ratio of the blend components [RF Patent 2035482].

The disadvantage of this method is the low stability over time of technological properties of the resulting mastic.

Closest to the claimed vibration mastic on essential features is vibration-absorbing resin, described in the patent of the Russian Federation 2044016 (IPC6C 09 D 131/04, publ. 20.09.95). Vibration-absorbing resin contains, wt%: 3 is th particle vermiculite (VM), 2,014,5 M, 0,54,9 ABP.

The resulting paste has a stable technological properties for three to five months, and formed from it for a specified period of time damping coatings are characterized by a complex of high values vibroacoustic, adhesive and fire performance.

However, the increase of storage period of vibration of the postmark of the composition of more than three to five months accompanied by a significant decrease in sperm motility, zagustevanii and associated above-described negative consequences - complexity unloading mastic from the storage tanks, the need for extensive and intensive mixing of mastic after storage for preparation to use, the reduction of 2530% vibroacoustic damping performance coatings. According to the requirements of consumers vibration mastic guaranteed shelf life shall be not less than twelve months and therefore the task of further improving the stability of its technological properties remains one of the most urgent.

Mastic prototype produced by entering PVAD under stirring ABP, plasticization PVAD of platifina is Italia flaky particle shape - VM when the above ratio of the blend components [RF Patent 2044016].

However, the described method does not provide the receiving mastic, preserving stable their technological properties within 12 months.

The technical result, which provides the inventive vibration-absorbing resin, is to increase the stability of the technological properties of the vibration-absorbing putty in time.

This technical result is achieved due to the fact that the vibration-absorbing resin, comprising the aqueous polymer dispersion based on vinyl acetate (dry residue 4060 wt.%), the plasticizer, AT, M and filler flaky particle shape, additionally contains tetramethylthiuramdisulphide (TMT), in the following ratio of components (wt.%):

Aqueous dispersion of a polymer based on vinyl acetate (dry residue 4060 wt.%) - 37,356,5

Plasticizer - 0,56,5

Chalk - 2,99,9

Nepheline flame retardant - 14,018,0

Filler flaky particle shape - 20,030,0

Tetramethylthiuramdisulphide - 0,10,5

As an aqueous polymer dispersion based on vinyl acetate vibration-absorbing resin may contain an aqueous dispersion of homopolymer vinyl acetate (PvdA with dibutylamine (PVMD), or aqueous dispersion of a copolymer of vinyl acetate with butyl acrylate (SABAD).

As a plasticizer vibration-absorbing resin may contain DBP, TAG, or a mixture of dioxane alcohols and their high-boiling esters (plasticizer ADOS).

As filler flaky particle shape vibration-absorbing resin may contain VM or KG.

Vibration-absorbing resin may optionally contain a viscosity regulator - water in the amount of 530% by weight of the mastic regulator density hollow glass microspheres in the amount of 15% by weight of the mastic, and a substance that improves the ability of the mastic to the sputtering, for example, surfactant anionic or mixed type in the number 0,050,1% by weight of the mastic.

The technical result, which provides the inventive method of obtaining the vibration mastic, is to increase the stability of the technological properties of the vibration-absorbing putty in time.

This technical result is achieved due to the fact that the method of obtaining the vibration mastics, including plasticization of an aqueous polymer dispersion based on vinyl acetate plasticizer and the subsequent introduction of the of an aqueous polymer dispersion based on vinyl acetate it is administered consistently M, ON and additionally TMT spend the homogenization of the resulting composition for at least 30 minutes, then injected with scaly filler particle shape and continue mixing the components to obtain a homogeneous mass with a ratio of the blend components as indicated above.

Auxiliary components, such as water (viscosity regulator) in the amount of 530% by weight of the mastic, microspheres (charge density) in the amount of 15% by weight of wax, surfactant (the regulator's ability mastic to sputtering) in the amount of 0,050,1% by weight of the mastic will be applied mastic after loading and mixing of all components of the mastic, the homogenization of the mass should be performed within 1530 minutes at room temperature.

It is known [Chemical encyclopedia, ed. "Soviet encyclopedia", M, 1988 , T. 1, page 162] the use of tetramethylthiuramdisuphide as a crosslinking agent or accelerator of sulfur vulcanization of rubber, and as a fungicide. However, with the introduction of vibration mastic TMT not only reduces the mobility grout (i.e., cross-linking does not occur), but on the contrary increases the stability of its technological properties in time - mastic does not lose movably which such vibration-absorbing properties of mastics based on the previously known properties of TMT was not possible.

In accordance with the inventive method to achieve the best indicators of the stability of the technological properties of mastic TMT imposed after the plasticization an aqueous polymer dispersion based on vinyl acetate and mixed with M and ON. Introduction TMT in the dispersion prior to its plasticization, or plasticized polymer dispersion based on vinyl acetate prior to the introduction of M and ON, or before putting ON or in a mixture of plasticized polymer dispersion based on vinyl acetate with all loose components does not allow saving technological properties of mastic in time (motility after storage for 1 year falls approximately 23 times (see our test examples 11-14).

Reduction of time combining mixture (plasticized polymer dispersion based on vinyl acetate + M +ON) with TMT less than 30 minutes, for example, within 15 minutes, leads to a noticeable deterioration of technological stability vibration mastic (see our reference example 15).

Introduction TMT in the amount less than 0.1 wt.%, for example, in amounts of 0.05 wt. %, does not improve the stability of the technological properties of the vibration-absorbing mastic (see our reference example 16), and the introduction of TMT in the amount of more than 0.5, for example Rakushechnoye characteristics (coefficient of mechanical losses and the dynamic modulus of elasticity) begin to decline sharply (see our test case 17).

To obtain the claimed mastic and implementation of the proposed method use industrial and pilot mark aqueous polymer dispersions based on vinyl acetate - coarse PVAD, for example, D50 (dry residue 5051 wt.%), D (dry residue 60 wt.%), D (dry residue 40 wt.%) according to GOST 18992-80; D50 (dry residue 5051 wt.%) on THE other 6-05-041-963-88; PVAD, obtained by dispersion in water redispersible powder of polyvinyl acetate (RPPA) TU 6-05-041-811-84; dispersion of a copolymer of vinyl acetate with ethylene (SWED) TU 2241-042-00203521-98; dispersion of a copolymer of vinyl acetate with dibutylamine (PVMD) TU 2241-039-00203521-98; dispersion of a copolymer of vinyl acetate with butyl acrylate (SABAD). KG used in accordance with GOST 5279-74; - in accordance with THE 6-08-340-76, VM in accordance with THE 21-0281916-1-88 and GOST 12865-87; M in accordance with GOST 12085-73; TMT - in accordance with GOST 740-76; DBP - in accordance with GOST 8728-77; TAG in accordance with THE 6-05-05-317-85; plasticizer EDOS in accordance with THE 2493-003-13004749-93.

As Governor density mastics and coatings used, for example, hollow glass microspheres finished grade "MS-A9" beyond 6-48-108-94, as well as substances that improve the ability of the suit is the STV Volgoneft on OST 6-01-35-79 or surfactant mixed type "emulsifier-10".

The resulting vibration mastic depending on viscosity can be applied to temperame surface methods spacelane (mobility mastic 810 cm) or spraying (when mobility mastic 12,515 cm).

The invention is illustrated by the following examples, but is not limited to them.

Example 1.

Vibration-absorbing resin was prepared in the industrial vertical mixer brand MVA-3000 capacity 3 m3using combined (combination of vertical and horizontal) mixing mode with speeds of 36 and 72 Rev/min the Temperature of the reaction mass supported by supply hot or cold water in the jacket of the mixer. The first stage in the apparatus was loaded 373 kg PVAD brand D50 and 43 kg DBP and within 30 minutes was performed combining these components. In the second phase in the dispersion by means of a screw feeder, which ensures uniform preset speed the flow of powdered ingredients, downloaded 99 kg M 180 kg, 5 kg TMT and within 30 minutes was carried out at 20oWith the homogenization of the composition. At the third stage in the mixer load 300 kg, 50 kg of water and within 30 minutes was performed okonchatelnuyu unloaded in large plastic barrels with a capacity of 60 HP One of the barrels put in storage for 12 months (temperature 2015oWith the pressure 76030 Torr, the relative humidity 7010%).

The resulting mastic, freshly prepared and after storage for 12 months, analyzed, determining its technological properties, and properties derived from it damping coatings.

Damping coating formed by applying a mastic temperame surface method spacelane. The coating was dried at 20oC for one day.

The tests were carried out in accordance with the following methods:

1. Technological properties of mastics:

- determination of the mobility of mastic according to GOST 5802-86;

- define measure thixotropy for TTP 743.4152-027-88;

- determination of density of mastic on THE 2243-038-00203521-97.

2. The damping properties of coatings:

- determination of temperature-frequency characteristic of the ratio of the mechanical energy loss of Flexural vibrations of plates, damped coating - for guidance 74-0109-25-80. The size of the plates - 750500(4-6) mm or 300150(1,5-2) mm Material plates - steel. Method of coating: the standard production schemes and regulations;

- definition wide-angle is 243-038-00203521-97;

- determination of the Flammability of the material damping coatings according to GOST 12.1.044-84;

- determination of the coefficient of thermal conductivity of the coating according to GOST 23630.2-79.

The composition, conditions of preparation, properties of mastic and formed from it the damping coatings according to example 1 and subsequent examples are presented in tables 1-4.

Examples 2-6.

Vibration mastics were prepared and tested as in example 1, but varying the time and temperature combination TMT with a mixture (PVAD + M + ON), and the ratio of components in the mastic in the claimed range.

In addition to the main components in mastic added accessories:

the viscosity regulator (water) in an amount to provide a given level of mobility mastic, which in turn determines the method of applying a material on tempereau surface (plating or spacelane) - added in the mastic in examples 2-6;

- control the density of mastics and coating (glass hollow microspheres finished grade "MS-A9" beyond 6-48-108-94) in an amount to provide a given level of density, was added to the resin in example 5;

- a substance that improves the ability of the mastic to the coating (Volgoneft on About the examples and forth from mastics, having mobility 810 cm, the coating was obtained by the method of spacelane and mastics with mobility 12,515 cm, the coating was obtained by spraying.

Examples 7-9.

Vibration mastics were prepared and tested as in example 1, but as an aqueous polymer dispersion based on vinyl acetate used 455 kg BW of an aqueous dispersion of a copolymer of vinyl acetate with 8-10 wt.% ethylene - SWED (example 7), or 455 kg BW of an aqueous dispersion of a copolymer of vinyl acetate with 35 wt.% dibutylamino - PVMD (example 8), or 475 kg BW of an aqueous dispersion of a copolymer of vinyl acetate with 50 wt.% the acrylate - SABAD (example 9), whereby in the first case as a plasticizer used 25 kg of glycerol triacetate (example 7), the second 25 kg of a mixture of dioxane alcohols and their high - boiling ester plasticizer ADOS (example 8), and in the third - 5 kg DBP (example 9).

Example 10.

Vibration-absorbing resin was prepared and tested as in example 1, but instead ready PVAD used PVAD, obtained by dispersion in water RPPA. For this purpose, in the apparatus with a capacity of 1 m3fitted with a stirrer and a jacket, poured 215 liters of water, and then when the stirrer for 20 minutes covered 215 kg RPPA. The temperature in aparecen 72 hours was performed by ripening the dispersion, including a mixer for 15 minutes every 6 hours. Next, the resulting dispersion CPVA transferred to the mixer and made of vibration-absorbing resin according to the method described in example 1.

Examples 11-14 (control).

Vibration-absorbing putty was prepared according to example 1, but changing the order of introduction of TMT composition.

Example 15 (control).

Vibration-absorbing resin was prepared according to example 1, but with TMT previously introduced components were combined in 15 minutes.

Examples 16-17 (control).

Vibration-absorbing putty was prepared according to example 1, but TMT was introduced in the amount of 0.05 wt.% (example 16) and 0.65 wt.% (example 17).

Examples 18-20 (control prototype and analogues).

Vibration mastics were prepared analogously to example 1, but using ABP instead of TMT and introducing ABP in PVAD before plasticization (example 18 to prototype - RF patent 2044016), or by entering ABP in a mixture of plasticized PVAD and all loose components (example 20 to the analog - Pat. RF 2035482); in example 19 to the analog - ed. mon. The USSR 1451150 not enter neither MST nor ABP, and does not enter M

Examples 21-23.

Vibration mastics were prepared and tested as in example 1, but COI is part did not enter.

Funginertness all mastics for examples 1-20 is 4-5 points according to method B in accordance with GOST 13410-67.

As shown in tables 1-4 data, the inventive vibration-absorbing resin obtained by the present method has a stable technological properties within 12 months, while the famous mastic after 12 months of storage are no longer suitable for use: their mobility decreases in 23 times. Vibro-acoustic damping characteristics of the coatings formed from the inventive vibration mastic, which were stored 12 months, virtually unchanged compared with the same coating of fresh putty, while the famous mastic after storage for 12 months form the damping coating with vibroacoustic characteristics below 2530%.

1. Vibration-absorbing resin, comprising the aqueous polymer dispersion based on vinyl acetate (with a dry residue of 40-60 wt.%), plasticizer, nepheline flame retardant, chalk and filler flaky particle shape, characterized in that it further contains tetramethylthiuramdisulphide in the following ratio, wt.%:

Aqueous dispersion polimery fire retardant - 14,0-18,0

Filler flaky particle shape - 20,0-30,

Tetramethylthiuramdisulphide - 0,1-0,5

2. Vibration-absorbing resin under item 1, characterized in that an aqueous polymer dispersion based on vinyl acetate, it contains the aqueous dispersion of homopolymer vinyl acetate, or a water dispersion of a copolymer of vinyl acetate with ethylene, or an aqueous dispersion of a copolymer of vinyl acetate with dibutylamine, or aqueous dispersion of a copolymer of vinyl acetate with butyl acrylate.

3. Vibration-absorbing resin under item 1, characterized in that it contains plasticizer dibutyl phthalate, or triacetate of glycerol, or a mixture of dioxane alcohols and their high - boiling ester plasticizer EGOS.

4. Vibration-absorbing resin under item 1, characterized in that the filler with scaly form of particles it contains crystalline graphite or vermiculite.

5. Vibration-absorbing resin according to any one of paragraphs.1-4, characterized in that it further comprises a viscosity regulator - water in an amount of 5-30% by weight of the mastic.

6. Vibration-absorbing resin according to any one of paragraphs.1-5, characterized in that it further comprises a controller density hollow glass microspheres in the number who omnitele contains the substance improving the ability of mastic to the coating, for example a surfactant of anionic or mixed type, in a quantity of 0.05-0.1% by weight of the mastic.

8. The method of obtaining the vibration mastic under item 1, including plasticization of an aqueous polymer dispersion based on vinyl acetate plasticizer and subsequent introduction to it under continuous stirring nepheline flame retardant, chalk and filler flaky particle shape, characterized in that after completion of the plasticization an aqueous polymer dispersion based on vinyl acetate in her consistently give chalk, nepheline flame retardant and advanced tetramethylthiuramdisulphide, conduct homogenization of the resulting composition for at least 30 min, and then injected with scaly filler particle shape and continue mixing the components to obtain a homogeneous mass.

9. The method of obtaining the vibration mastic under item 8, characterized in that after mixing all components of the mastic into it further added viscosity regulator - water in an amount of 5-30% by weight of the mastic and continue homogenization mastic within 15-30 minutes

10. The method of obtaining the vibration mastic under item 9, characterized in that ppary in the amount of 1-5% by weight of the mastic and/or substance improving the ability of mastic to the spraying - surfactant anionic or mixed type in a quantity of 0.05-0.1% by weight of the mastic and continue homogenization mastic within 15-30 minutes

 

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FIELD: fireproof paint-vehicle protective materials.

SUBSTANCE: claimed paint contains polymeric binder, solvent and blowing additive consisting of pentaerythritole and ammonium polyphosphate at ratio of 1:1.3-2.6, respectively, and in addition expanded graphite. Materials of present invention useful in building industry, aviation, railway transport, etc.

EFFECT: paint with improved functionality, increased fire resistance, and expanded blowing temperature interval.

3 cl, 4 ex, 2 tbl

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