Polymer composite material

 

(57) Abstract:

Describes a polymer composite material including a thermoplastic polymer and svetasmilygirl mixture, characterized in that as sitosterolaemia mixture contains a mixture of sour steric obstruction of phosphite, polymeric macromolecular sterically constrained amine and low molecular weight sterically constrained amine in a ratio of components of the material, by weight.h.: thermoplastic polymer 100; sour sterically hindered postit - 0,01-1,0; high molecular weight sterically hindered amine - 0,01-1,0; low molecular weight sterically hindered amine of 0.01 to 1.0. The technical result is the production of a material with high resistance to UV radiation. 1 C.p. f-crystals, 1 table.

The invention relates to the production of composite materials based on thermoplastic polymers used for the manufacture of structural parts of the destination to which the requirements are higher resistance to UV radiation (external parts of the car interior, and others).

Known thermoplastic material based on polybutylene terephthalate or polyethylene terephthalate, or other thermo is phosphite (North-West branch) and 0.0005-0.005% aliphatic polyamine (PA) (US, patent 5514742, NCI 524-119,1996). The authors believe that the North-West branch decomposes under the action of UV radiation, and the resulting acid postit - NWPC leads to yellowing of the polymer. To prevent decomposition of the North-West branch impose polyamine, which, according to the authors, performs the function of the stabilizer Stakhanov Ferroalloy plant. Thermoplastic polymeric materials containing as light stabilizers mixture Stakhanov Ferroalloy plant and PA, are characterized by higher light fastness when exposed to UV radiation with a wavelength of <300 nm. Its use is recommended for the manufacture of bottles, films, or sheets.

In the technical solution (Application 2278362, UK, C 08 K 5/524, 1994) proposed to add steric employed amines (HALS) and ZnO to the North-West branch in the amount of 0.05-15 wt.h. to improve hydrolytic stability of phosphite. It is known that the Stakhanov Ferroalloy plant in a humid atmosphere hydrolyzed with the formation of phenol and acid phosphite. The authors believe that sour postit can have a negative impact (up to intensifitsirovany decomposition reactions) on a polymeric matrix as in the unfilled thermoplastic and composite material processing extrusion method. The result of the decomposition reactions is the discoloration of the polymer from yellow to to the second recipe, after a single, a triple and 5-fold extrusion is not changed.

The closest in technical essence is a technical solution (UK, application 2315070, C 08 K 5/00, 1998), which offers organic materials with high thermal-oxidative stability and lightfastness dealt with the introduction on the stage of triple extrusion of a mixture of HALS (0.1-10%), derivatives of Ketobemidone (0.0005-5.0%) and the North-West branch (0.1-10%). The resulting materials are characterized by the stability of the melt index and retain color (yellowness index) after ageing under the effect of the xenon lamp. The proposed stabilizing system is used to obtain fiber polymeric materials with increased resistance to UV radiation and thermal-oxidative aging in air at elevated temperatures (100oC).

In all the above patents, there is no data on physico-mechanical properties and change the strength properties in the process of accelerated aging under the action of UV radiation. There is no doubt that the first sign of destructive changes in polymeric materials is yellowing as a result of the accumulation of carbonyl groups in the polymer structure. This'hara is 1680 cm-1(according to IR-spectroscopy). The authors compare the irradiated composition according to the appearance of carbonyl groups in the structure of PP after irradiation. Even given that, refer to the technical solution according to the prototype of the examples refer to the PP fiber, lack of durability not give a complete picture about the impact of used additives on the properties of the composition. Although the technical solution proposed to use other thermoplastic materials, there are no examples related to the stabilization of other thermoplastics.

The present invention is to develop composizioni materials based on thermoplastic polymers with high resistance to UV radiation.

This object is achieved by the introduction in the composition of thermoplastic polymer mixture consisting of acidic steric obstruction of phosphite (NWPC) in an amount of 0.01-1.0 wt.h., polymer of high molecular weight sterically constrained amine (HALS) in an amount of 0.01-1.0 wt.h. and low molecular weight sterically constrained amine (HALS) in an amount of 0.01-1.0 wt.h. on 100 wt.h. thermoplastic polymer.

The proposed composite material may additionally contain conventional Celebi and in the amount of 10-50 wt. o'clock, the pigments in amounts of 0.1-5 wt. h, plasticizers in amounts of 0.1-5 wt. h, nuclearmoose agents in amounts of 0.01-1.0 wt. hours and other technological additives introduced in similar materials.

As thermoplastic polymer may be used a polyester type polyalkylacrylate, polycarbonate, polysulfone, polyetherketone, polyetherimide and others , as well as aliphatic, aromatic and aliphaticheskie polyamides, thermoplastic polyimides, polyamidoimides their mixtures and/or alloys, and other thermoplastic polymers. These thermoplastic resins may contain or not contain basic "oven" system, usually consisting of a phenolic antioxidant, such as Irganox 1010, Irganox 1076, Irganox 1098, sterically hindered postit, such as Irgafos 168, Irgafos 12, Irgafos IPPD, or a mixture of phenolic antioxidant and steric obstruction of phosphite, for example Irganox B1171, lrganox B225, Irganox B215 production Ciba, or other known antioxidants.

As acidic steric obstruction of phosphite (NWPC) may be used in connection with the General formula

< / BR>
or (RO)2-P-OH,

or

< / BR>
where R and/or R1- H, alkyl, aryl, or their halogen derivatives, but so that the structure of the is about Amin (HALS) may be used in connection with a molecular weight of up to 1,000, containing in the structure fragments

< / BR>
where R is H, alkyl, aryl and/or their halogen derivatives,

for example,

Bis 1,2,2,6,6-tetramethyl-4-piperidyl sebacina;

Bis 1,2,2,6,6-pentamethyl-4-piperidyl sebacina;

Di-(1,2,2,6,6-pentamethyl-4-piperidyl)-butyl-(3', 5'-di-tertbutyl - 4-oxybenzyl)-malonate;

2,2,4-tetramethyl-21-oxa-3,20-diazo-despero[5,1,11,2]- heneicosane-20-dodecyloxy ether propionic acid;

2,2,4,4-tetramethyl-7-oxa-3,20-diazo-despero[5,1,11,2]- heneicosan-21-he and other

As a polymer of high molecular weight sterically constrained amine (HALS) may be used in connection with a molecular weight of from 1000 to 3500, containing in the structure fragments

< / BR>
where R is H, alkyl, aryl and/or their halogen derivatives,

for example,

Poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-oxopiperidin succinate);

Poly-{ [6-[(1,1,3,3-TETRAMETHYLBUTYL)-imino]-1,3,5-triazine-2,4 - diyl][2-(2,2,6,6-tetramethylpiperidine)imino]};

1,3,5-triazine-2,4,6-triamine,N,N"'-[1,2-ethane-diyl-bis[[4,6 - bis[butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-1,3,5-triazine - 2-yl]imino] -3,1-propanediyl] and others

The proposed polymer composition along with the above components may contain well-known conventional additives, such as SUB>2, Fe3O4, Cu(Cr, Fe)2O4, Fe2O3and others), plasticizers (essential and/or platogo type and others), nuclearmoose agents (benzoate alkali metal derivatives of sorbitol and others), and other processing additives. The invention is illustrated by the following examples, not limiting the essence of the proposed technical solutions.

Example 1.

The composition in wt.h.: PBT brand Crastin the DuPont company - 100; sour SSPC - 0.25; low HALS1 - 0.25; high-molecular HALS1 - 0.25.

Stabilizers are mixed in the mixer small additives. Using the dispenser additives previously prepared mixture of stabilizers supplied in the feed zone of the extruder simultaneously with the dispensing of the base polymer or separately to the polymer in the following loading area, i.e. already in the polymer melt. The roving or granulated fiberglass dosed in polymer melt. The extrusion is conducted according to the standard mode for PBT:

Temperature zones 180-260oC

Additives stabilizers can also be pre-mixed with dispersed fillers (talc, mica, or a mixture thereof) and not be dosed into the loading area together with primenenie samples by the method of injection molding.

Temperature casting:

240-260oC, the temperature of the molds 85oC.

Physico-mechanical tests carried out on the following standards:

Flexural strength - according to GOST 4648

Tensile strength - according to GOST 11262

Impact strength Charpy samples without cut - according to GOST 4647

Accelerated aging under the action of UV radiation was carried out in the device Xenotest 150 (radiation source is a xenon lamp) at a temperature of a black plate 80oC for 3000 hours. The resulting properties are presented in the table.

Example 2. The composition in wt.h.: PBT brand Crastin the DuPont company - 100; fiberglass RBN 10-2560-76 "T" - 43; sour SSPC - 0.01; low HALS2 - 0.01; high-molecular HALS3 - 0.01.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 3. The composition in wt.h: PBT brand Crastin the DuPont company - 100; fiberglass RBN 10-2560-76 "T" - 43; sour SSPC - 1.0; low HALS3 - 1.0; macromolecular HALS3 - 1.0.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 4. The composition in wt.h.: PBT brand To ularly HALS2 - 0.25; pigment (carbon black) GOST 7885 - 0.1.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 5. The composition in wt.h.: PBT brand Crastin the DuPont company - 100; fiberglass RBN 10-2560-76 "T" - 43; sour SSPC - 0.25; low HALS3 - 0.25; high-molecular HALS1 - 0.4.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 6. The composition in wt.h.: PBT brand Crastin company DuPont thermally stabilized JSC Irganox 1010 (0.1) + North-West branch of Irgafos 168 (0.4) - 100; fiberglass RBN 10-2560-76 "T" - 43; sour SSPC - 0.25; low HALS1 - 0.25; high-molecular HALS1 - 0.25.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 7. The composition in wt.h.: PBT brand Crastin the DuPont company - 100; fiberglass RBN 10-2560-76 "T" - 43; sour SSPC - 0.3; low HALS3 - 0.3; high-molecular HALS2 - 0.2; pigment (TiO2) GOST 9808 - 0.5.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 8. The composition in wt.h.: PBT brand Crastin the DuPont company - 100; the x2">

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 9. The composition in wt.h.: CRP brand PC-2 TU 6-05-1668 - 100; fiberglass RBN 10-2560-76 "T" - 43; SSPC - 0.05; low HALS2 - 0.05; macromolecular HALS2 - 0.05.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 10. The composition in wt.h.: PA6 brand 210/310 OST 6-05-09 - 100; fiberglass RBN 10-2560-76 "T" - 43; SSPC - 0.15; low HALS2 - 0.15; high-molecular HALS2 - 0.15.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 11 (comparative). The composition in wt.h.: PBT brand Crastin the DuPont company - 100.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 12 (comparative). The composition in wt.h.: PBT brand Crastin the DuPont company - 100; fiberglass RBN 10-2560-76 T - 43.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Example 13 the prototype. The composition in wt.h.: PBT brand Krestintern - 0.005.

Preparation of a composition similar to the description of example 1, the resulting properties are presented in the table.

Patterns additives

Sour steric employed phosphites (NWPC) - the products of hydrolysis industrial secondary antioxidants:

SSPC - Irgafos 168, Ciba

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SSPC - Irgafos DDPP, Ciba

< / BR>
SSPC - Irgafos 126, Ciba

< / BR>
SSPC - Stator 11, NAIMPALLY

< / BR>
Low molecular weight sterically difficult amines - industrial products:

HALS1 - Tinuvin 765, Ciba

< / BR>
Mw=508

HALS2 - Tinuvin 770, Ciba

< / BR>
Mw=481

HALS3 - Hostavin N20, Hoechst

< / BR>
Mw=364

HALS4 - product laboratory syntheses

< / BR>
Mw=502

Macromolecular sterically difficult amines and industrial products companies:

HALS1 - Tinuvin 622, Ciba

< / BR>
Mw=2500

HALS2 - Chimassorb 119, Ciba

< / BR>
Mw=2286

HALS3 - Hostavin N24, Hoechst

< / BR>
Mw=1500

HALS4 - Chimassorb 944, Ciba

< / BR>
Mw=compiled between 2,600 and 3,000

The table shows that the results obtained by the proposed invention composite material compared to the prototype is characterized by a higher physical and mechanical properties (strength Flexural and impact strength) before aging. After aging for 3000 hours under the action of UV radiation in the device Keilany material, received the prototype, during UV aging yellow, which is accompanied by reduction of physical and mechanical characteristics.

1. Polymer composite material including a thermoplastic polymer and svetasmilygirl mixture, characterized in that as sitosterolaemia mixture contains a mixture of sour steric obstruction of phosphite, polymeric macromolecular sterically constrained amine and low molecular weight sterically constrained amine in a ratio of components of the material, by weight.h.:

Thermoplastic polymer 100

Sour sterically hindered postit - 0,01 - 1,0

High molecular weight sterically hindered amine - 0,01 - 1,0

Low molecular weight sterically hindered amine of 0.01 to 1.0.

2. Polymer composite material under item 1, characterized in that it contains a special additive in an amount of 0.1 - 60.0 sec wt.h.

 

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