SU1754742A1 - Polymeric composition and method of its manufacture - Google Patents

Abstract

The invention relates to polymeric compositions based on high-impact polystyrene, namely to a low-impact high-impact integrated polystyrene foam containing bromohydric fire retardant decabromodiphenyloxide, antimony trioxide, divinyl styrene tetrabromodiphenylolpropane, flame retardant oxide, antihyrene, antihyrene, antimony polystyrene, antimony polystyrene, antimony polystyrene, antibiotic polystyrene. ), and the method of its preparation, involving the introduction of a complex of all additives into the polymer in the form of a granulated concentrate based on a thermoplastic elastomer directly during the processing of the polymer into an article, P zrabotanny high tech material during processing by injection molding, melt index 32 g / 10 min, has a toughness higher than the starting polymer layer is 30-50% and is characterized by a high degree ognezaschischen- NOSTA (Y-0) by the standard UL-94. 3 tab.

Description

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The invention relates to polymeric compositions based on styrene plastics, in particular to slow-burning, impact-resistant integral polystyrene foams. which can be used to manufacture fire-resistant products used in construction, television and radio, and other areas of national economy,

A composition based on high impact polystyrene (77-95%), comprising 3-10% thermoplastic elastomer (copolymer 80: 20-20: 80 styrene and butadiene), 2-15% chlorinated polyethylene (CI-25-50%) is known. 5-20% DBDFO and 1-10% antimony tri-oxide, when all additives are introduced by coextrusion with the main polymer.

However, the known composition has a low thermal stability during processing due to the presence of chlorinated polyethylene and low melt flow.

A known composition based on suspension impact polystyrene, comprising divinyl styrene thermoelastlast 6–8 wt.%., Decabromobiphenyloxide 10–12 wt.%, Antimony trioxide, 1.5–6 wt.% Zinc stearate, 0.3–0, 6 wt.%, Introduced at the stage of coextrusion with the main polymer.

The addition of additives provides a high level of fire retardancy and thermal stability, but the composition has low melt flow.

The closest in technical essence and the achieved result to the claimed invention is a composition for a slow-burning, impact-resistant integral polystyrene foam, comprising.

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to

mac.h .: high impact polystyrene containing 4-12% butadiene rubber 100; thermoplastic elastomer (copolymer of butadiene or isoprene with 10-70% styrene) 2-10; organic derivative containing 30% or more halogen (hexabromocyclododecane, oxbromhexadecane, chlorinated paraffins (70% chlorine), chlorinated or brominated diphenyl or naphthalene) 5-30, saturated polyol C4-C 12 with 4-12 hydroxyl groups (pentaerythritol) 0-3; organic phosphite (trnnonylphenylphosphate) 0.05-3; . substituted bentriazole 0-1; H. space-borne phenol 0-1, and may also contain additives such as a foaming agent, ng fillers, pigments, lubricants in an effective amount (prototype). The introduction of the above complex of additives provides a high level of fire retardancy and thermal stability in the case of DBDPO, however, the composition has a low melt flow.

The method of preparation of the composition (prototype) consists in pre-mixing the powdered flame retardants with each other, then mixing them with impact-resistant polystyrene and extrusion, followed by granulating the polymer composition, applying the powdered foaming agent to the surface of the obtained slow-burning polymer by mixing them and using the resulting composition for obtaining an integral foam by injection molding.

The disadvantage of this method is the complexity of the technology for producing a slow-burning, impact-resistant integral foam, due to the multistep process and the need to double-process the entire volume of the polymer.

The purpose of the invention is to improve the processability of the material during processing by increasing the melt flowability of the composition, increasing the impact strength and simplifying the technology for producing slow-burning impact-resistant polystyrene foam.

This aim is achieved by the use of the proposed composition on OS- Nove impact polystyrene, thermoplastic divinilstirolnogo, dekarbromdifenyTyuksida, antimony trioxide and a blowing agent, a distinguishing feature of which is that it additionally contains a product oligocondensation diglycidyl ether tetrabrom- diphenylolpropane (DETBDFP) with aniline in a molar the ratio DATBDPA and

3.0-10.0

2.0-13.0 3.0-9.0

5.0-9.0 0.2-1.0

aniline, respectively, 1: (0.10-0.95) of the general formula Vg Vg

sn ph-cn | o- -c- -o-sn2Ch

0 (op Vg ch3 vg

-CH-CH2-N-CH2-CH-CH2 | OH vg ch3 Vg -In

- ochEn with o-ns, - dn,

 I - (s

Vg CH3 Vg °

where, 2-7,0,

when the ratio of the components of decabromodiphenyl oxide: oligocondensation product DETBDPA + A 80: 20-20: 80 (May.%), in the following ratio of components of the polymer composition, wt.%:

Decabromobiphenyl oxide

Product oligocondensation DETBDFP + A

Antimony trioxide

Divinylstyrene

thermoplastic elastomer

Blowing agent

High impact polystyrene Else

The composition may additionally contain heat stabilizers to increase the thermal stability of the polymer under processing conditions, a wetting agent - to fix the powder components of the composition on the surface of impact polystyrene granules, pigments or pigment superconcentrates - to color the material in bulk.

The goal is achieved using the proposed method of obtaining the proposed composition comprising mixing the flame retardants and thermoplastic elastomer with impact resistant polystyrene, extruding and granulating the composition, mixing the granules of the polymer composition with a foaming agent, characterized in that, prior to the introduction of additives into the polymer, a granular concentrate consisting of from powdered components and diphenylstyrene thermoplastic elastomer as a binder, and then the impact resistance is mixed polystyrene with granules of a concentrate of additives and used for further processing into products. The oligocondensation product DETBDPA + A of formula I is a brittle transparent melt of light yellow color, the main characteristics of which, depending on the ratio of DETBDPA: A, are listed in Table 1 (the content of epoxy groups, bromine, softening temperature, temperature of the onset of destruction, molecular weight ).

The proposed additive has a high thermal stability-temperature

the beginning of decomposition according to DTA is 285-300 ° C (at the level of DBDFO), it is well combined with the polymer and does not migrate from the composition.

- .The structure of the obtained oligombra is proved by the method of IR-spectroscopy and functional analysis. In the PC spectrum of the compound, there is practically no absorption band in the region of 3430, which is characteristic of the asymmetric O – V stretching vibration of the N – H bond in primary aromatic amines. The determined practical content of epoxy groups corresponds to the theoretical one calculated under the condition of the interaction of two reactive hydrogen atoms in the amine.

Example 1. In the reactor, 65.6 g of tetrabromodyphenyl-propane glycene ester are mixed with an initial content of epoxy groups of 12.36% and 0.93 g of aniline (mol / mol ratio: 0.5 is heated to 100 ° C and kept under stirring. for 6 hours. At the end of the product, the melt of the product is poured onto the substrate. The frozen, fragile, amber-colored mass is crushed and used to modify the polymers.-: ;;

66.53 g of substance are obtained, the characteristics of which are given in table. one.

Examples 2-5 are carried out in accordance with Example 1, but a different molar ratio of the reactants is used (Table 1).: ;;,

Example 6 A polymer composition is prepared by mixing powder components (DBDPO flame retardant, oligocondensation product DETBDPA + A, antimony trirxide, foaming agent, pigments and

. td -), -. . : ...:

Prepare a concentrate of additives based on a thermoplastic elastomer in one of two ways:. . . ;. - -. ..- .-:; u -: - /.-/,:.::/

gradually introducing the powder mixture of additives into a thermoplastic elastomer on rollers at a temperature of 100 ° C for 5-7 minutes to obtain a uniform sheet material with a thickness of 2-3 mm and then grinding its granules with a size of 2-5 mm;

SoeksTrudyrOvaniya thermoplastic elastomer With powdered additives on a screw extruder at a temperature of 140 ° C and granulation strands on the granules of 2-5 mm.

The additive concentrate is mixed with granules of high impact polystyrene in a Z-type mixer and used

directly by processing in the product by injection molding; - Standard samples for i tests - bars (120x10x15 mm), logs (150x4 mm), bars (127x12,7x10-5 mm) are prepared using the 5-way standard method (very: |; casting time rubbed by the molten mold temperature) by zones 100-190-200 ° С.,; ,,,

Melt flow rates (MFR, in g / 10 min), determined at 200 ° C and load

0 5 kg on the device YYRT according to the standard method according to GOST 11645-73.

The tensile strength and elongation at break were determined according to GOST 11262-50 on samples in

5 blades (120x4 mm) on a FR-10 tensile machine with a clamp movement speed of 50 mm / min.

The flammability of the compositions was evaluated according to the standard UL-94, vertical test 94V

0 (flame height 19 mm, double ignition of the sample from the bottom for 10 s) on samples in the form of bars (127x12, 7x () mm).

The composition and characteristics of the properties of the resulting plastic are given in

5 tab. 2 and 3,

Examples 7-20 are carried out in accordance with Example 6, but different ratios of components are used (Tables 2 and 3). The proposed polymeric composition

0 and the method of its production allows to increase the melt flow rate by 2-5 times, the impact strength by 20-30% and the relative elongation at break by 30-50% while maintaining the fire resistance of the material

5. At the level of V-ti to UL-94. Preliminary receiving the granulated concentrate of additives consisting,: from fire-retarding agents, the modifier of durability, pigments, the foaming agent, and other

0 com / ynentov allows to ensure high technological effectiveness of processing the polymer composition (good dosing and transportability, no stratification of components, and, consequently, high

5 stability of composition and properties, no loss, improvement of working conditions and culture. production), the reduction of energy costs - no double processing ud-. durable polystyrene, associated with the introduction of flame retardants.

Fo rumula l 3 obre n i 1. Polymer composition, including high impact polystyrene, foaming agent, divinylstyrene

5 thermoelastic, decabromodiphenyl oxide, antimony trioxide, and tl and h so that, in order to increase melt flow and mechanical strength, it additionally contains the product of oligocondensation of diglycidyl ether tetrabromodiphenylolpropane with aniline at the Molar ratio of these reagents respectively 1: (0.10-0.95) of the general formula

-fH-CHrN-CHj-CH-CHjt OHBr CH, Br ™

CH3-C- -0-CHg-t-CH2

CH, BrО

Y

Vg

E.2-7.0 In the following ratio of components of the composition, wt.%:

Decabromobiphenyl oxide 3.0-10.0 The oligocondensation product of tetrabromodiphenylolpropane diglycidyl ether

with aniline

Antimony trioxide

Divinylstyrene

thermoplastic elastomer

Blowing agent

Shockproof

polystyrene

2.0-13.0 3.0-9.0

5.0-9.0 0.2-1.0

Rest

Characterization of the condensation products of tetrabromodiphenylolpropane diglycid ether with aniline

0

five

0

five

0

2. A polymer composition according to claim 1, characterized in that the ratio of decabromodiphenyloxide and the oligocondensation product of tetrabromodiphenylolpropane tetrabromodiphenylpropane and aniline oligocondensation is 80: 20-20: 80% by weight.

3. A method of obtaining a polymer composition, comprising mixing decabromodiphenyloxide, antimony trioxide, a thermoplastic elastomer with impact-resistant polystyrene, extrusion and granulation of the composition, mixing granules of the polymer composition with a foaming agent, which is designed to increase melt flow and mechanical strength , as well as simplifying the processing technology, before introducing additives into the polymer, they first obtain a granular concentrate consisting of powder components: a flame retardant, a product ligokondensatsii tetrabromdifenilolpropana diglycidyl ester with an aniline, antimony trioxide, based on blowing agent divinilstirolnogo thermoplastic elastomer as a binder, and then blended with high impact polystyrene pellets and additive concentrate for use in further processing of the article.

Table t

In examples 6-17, samples were obtained by injection molding a mixture of granules of the original polystyrene and the concentrate of all the additives introduced into the polymer based on a thermoplastic elastomer. Example 20 - plastic samples are obtained by dusting granules UPM OB12l foaming agent

Lrimer 18 - antipyrotic additives are introduced into the polymer by joint hardening, then granules of slow-burning material are powdered with a foaming agent and samples are cast.

Table) Characteristics of etoRcra natal

Indicator for example

(It is “a

 G PG 7TT; G G P5 PG Lr and Go T

J ILLJ JJ JLJJLJLJ-J J. J.

20

IJTSSSL / SS, 7.Sv, MMM ... SIIM ".3J0.77.5."

y / ilm strike 7. "7,". OM9.37.3 ".v", 79. "(9c, 77.5,6.35.8

 "1 5 3" 2J2015 8 6

 according to st "n" ib -0 -0 -2 V-0 V-0 WO G-0 V-Z V-0 V-0 V-0 V-0 V-0 Lit Lit

20

Claims (3)

Claim 1. A polymer composition, including high-impact polystyrene, a blowing agent, divinyl styrene thermoelast elastomeric, decabromodiphenyl oxide, antimony triaxide, which can be used to increase melt flow and mechanical strength. It additionally contains an oligocondensation product55 2.0-13.0 3.0-9.0 5.0-9.0 0.2-1.0 Rest To reduce melt flow and mechanical strength, as well as simplify the processing technology, before introducing additives into the polymer, a granular concentrate is preliminarily obtained, consisting of 20 powder components: flame retardant, the product of oligocondensation of diglycidyl ether of tetrabromodiphenylolpropane with aniline, and antimony triastolastenolopropylene based on 25 antioxidant as a binder, then high-impact polystyrene is mixed with granules of the additive concentrate and used for further processing into products. bo: ././//: 7-77 / 7- Table! Characterization of condensation products of tetrabromodiphenylolpropane diglycidyl ether with aniline Sample The ratio of DETVDPP and aniline Molecular mass The degree of oligomerization The content of epoxy groups,% T softening, * C The bromine content,% t onset of destruction .0.1% weight loss • •"a... 1 1: 0.10 ' 800 0.20 10.77 49-50. 48, ι o zoo / 2 1: 0.50 1510 1.16 5.71 88-90 45.75 295 3 1: 0.75 3050 3.26 2.83 105-108 44.35 292 4 1: 0.80 3900 4.42 2.20 / 116-118 44.10 290 5 1: 0.95 5590 7.02 1.54 ' 124-126 42.95 285 ABOUT 1 a 1 * ·· i 10) 5 1 Σ a t I X C £ l ι ё > q. . 4 .-- ..,) Oh FROM flj | g ABOUT oo u \ mid la i υ about * "> A t tn S about X N. N. -4 LA Q ί q With 10) a Η and a> o about ich * * * ABOUT • ICh +? about X N. CO * 4 * CHO about ί y CHZ b 0) and about about X Ν. 1 liter q ABOUT n f  - · ♦ " υ about ABOUT about X  I- > x 1 c X 1 dp 1 1 go = g t e) t Η <J> about oo la mid X t U 1 about 1 υ 0 'To' •to •to SO about 1 GO 1! Ϊ L * “ 1 ο X r>. N * -4 LA with Ζ i i eleven "1 1 1 L from 1 CO I 1 • q X 1 GO 1 I GO 1 TO 1 1 b <D about 3 1 U 1 t and 0 f. Id go b 1 οι σ> 1 about X LA <*% GL <m 1 't- □ iX- i 1 I <3 ! δ! I 1 J3 q <ϋ about LA silt 1 0 1 t about ro 0 A "to: 1 Σ '1 ί X' I 00 1 about H X Ό cm <h g- I Q. h -1 ! 1 c 1 C ’ L eleven X * q 1 t M go with j. eleven O | ί- £ a TO US .- eleven Ι- ο about ABOUT i i N Ο ' about X N. * · *4· 2. The polymer composition according to π. 1, στη and especially with the fact that the ratio of decabromodiphenyl oxide and the product of oligocondensation of diglycidal ether with tetrabaniline! 1754742 of diglycidyl ether of tetrabromodiphenylolpropane with aniline at a molar ratio of these reagents, respectively, of 5 romdiphenylolpropane c is 80: 20-20: 80 wt.%. 3, A method for producing a polymer composition, comprising mixing decabromodiphenyl oxide, antimony trioxide, 10 thermoplastic elastomers with high-impact polystyrene, extruding and granulating the composition, mixing granules of the polymer composition with a blowing agent, with the following ratio of components: that, with the aim of increasing the position, wt.%: Decabromodiphenyl oxide 3.0-10.0 The product of oligocondensation of diglycidyl ether of tetrabromodiphenylolpropane with aniline - / 7/7, - / ^l T antimony rioksid Divinilstirolny termbelastoplast impact polystyrene blowing agent but 1: (0,10-0.95) of general formula 77 'T * ^{CH Br} - / ^Br ί ^ CH-CH-0-sn4o s - <- O-CH _2' ' o (OR Br Br CH 'ONVg CH ₃ Br · J ⁿ¹ С-Q-o-cHfOi-cH, W СНз Вг · where η · = 0.2-7.0 3 g q >> X n 1 o Ι- g 1 - CL Ο 0 1 X IX q X 1 b Έ X 0 1 About I x from 1 x J X Σ 1 q O CD ABOUT too. X hi i s s 1784742 Tables a J lT? in 9 1 proto 1 example indicator Material characteristics Hara gagarie tika Pzhmeteli fluid tm of a melt "g / Yumin Specific impact yak mb nb Charlie notched, kDv / m * Losmtelmore ud / ’Dartu VHg94 (tolanna obrvzi 5 mm) ΊΛ "4 54 8Λ 25 ' 32 31.5 12 12.5 io, 3 30.7 7 4.5 m 7.4 74 m 7.2 93 7.3 4.8 4.7 9.1 4.9 4.7 7.5 4.4 4.3 $, and and 1S. ί ⁸ . '2® 27 19 fifteen thirteen 23 25 25 20 fifteen 18 16 "-0 V-0 V-2 v-o V-0 "-0 Vo V-2 v- o. v-o ν-Ό V-0 *? Burns Burns