CN1333009C - Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition - Google Patents

Abstract

The present invention relates to a composite heat stabilizer for a thermoplastic polymer containing a halogen element, particularly to a heat stabilizer for polyvinyl chloride and a derivation composition thereof. The heat stabilizer contains 1 to 80 parts by weight of hydrotalcite which is natural or is processed, 0 to 70 parts by weight of a compound based on calcium-aluminium-hydroxide radicals and at least polyol, and 0 to 70 parts by weight of the isocyanate of at least one group of hydroxyl radicals. The heat stabilizer, LDPE (polyethylene) and certain copolymerization vinyl chloride functional auxiliary agents are mixed to form the high grade derivation composition of the composite stabilizer, wherein the adding amount of the stabilizer is from 1 to 50%, the adding amount of the LDPE is from 30 to 70%, and the total adding amount of other various functional auxiliary agents is from 1 to 50%. The present invention is used for the processing of a PVC product. Compared with the previous product, the PVC product has high quality lasting weatherability and no fade, and has no foams when the PVC product is processed. The present invention is suitable for an outdoor PVC product.

Description

Composite heat stabilizer for polyvinyl chloride and derivative composition thereof

Technical Field The present invention relates to a composite heat stabilizer for thermoplastic polymers containing halogen elements, especially a heat stabilizer for polyvinyl chloride and its derivative composition.

Background Art With the continuous increase of thermoplastic polymer production, the consumption of its processing aids also increases. As one of the important categories, heat stabilizers are mainly used in the processing of polyvinyl chloride (PVC) products to prevent the products from being damaged by heat, oxygen and water during use, thereby prolonging the service life of the products.

It is known that halogen-containing polymers are susceptible to chemical decomposition reactions under the influence of ultraviolet rays, light and heat, thereby destroying their performance characteristics. Especially like polyvinyl chloride, it is easy to decompose in the presence of light, heat and water during the extrusion molding process, and such decomposition will cause the mechanical properties of the product to age and the coating to decompose. In order to avoid the decomposition reaction of the PVC polymer, it is necessary to make the stabilizer used act on the plastic polymer for a long time. At present, the heat stabilizers commonly used in polyvinyl chloride can be divided into lead salts, metal soaps, organic tin, organic antimony, liquid composite stabilizers and other auxiliary stabilizers.

Lead salt stabilizers are the earliest heat stabilizers used in PVC products, and are still used in large quantities, with low cost and excellent thermal stability (in some cases, they can also absorb ultraviolet rays), especially good long-term thermal stability, electrical insulation It has excellent performance, has the performance of white pigment, strong adhesion, and good weather resistance, but it is not suitable for use in occasions requiring no sulfur pollution, and it is not resistant to vulcanization, toxic, slightly poor in compatibility and dispersion, and the resulting product is opaque.

Organotin is also a very effective heat stabilizer, which can keep transparent products with high transparency and minimum dosage. Most organotins are poisonous, but some organotin heat stabilizers mainly composed of dioctyltin compounds are still allowed to be used with food. Stabilizers for contact products because of their low toxicity and good resistance to solvents. Mercaptan organotin, especially dialkyl mercaptan organotin, has the best stabilizing effect among existing heat stabilizers. It is suitable for all types and grades of PVC, but the cost is relatively high. Mercaptan organotin and lead salt The stable products are incompatible, mixing the two will cause the material to darken in color.

Metal soap heat stabilizers are usually used in the form of complex metal soaps, and the commonly used complex metal stabilizers are Ba/Cd and Ba/Cd/Zn stabilization systems. This stabilization system has both liquid and solid products. Their main disadvantages are that the stabilization effect varies with the type of PVC, it is easy to precipitate during processing, and it is sensitive to sulfur pollution, which does not occur in Zn-containing systems.

Although the production and development of heat stabilizers in our country have achieved quite good results, there are still many shortcomings and a large gap compared with the world's advanced level. (1) Few varieties, unreasonable structure, highly toxic, highly polluting, and low-grade lead salt stabilizers occupy an absolute dominant position, and the proportion of organotin is far lower than that of foreign developed countries; (2) The production scale is small , The product quality is poor; (3) The development efforts are not enough, and the funds invested are too small; (4) The production process is cumbersome and backward, duplicating labor, and the cost is increased.

As a large variety of general-purpose plastics, the output of polyvinyl chloride (PVC) has always been at the forefront in the polymer industry, and the development and production of heat stabilizers are closely related to the development of the PVC industry. Moreover, under the requirements of the international environment and environmental regulations, the current PVC heat stabilizer is developing in the direction of low toxicity-non-toxic and compound type. It has become an era to seek a new type of heat stabilizer to replace the toxic and dust-polluted stabilizer. development is inevitable.

EP-B-424572 discloses a method for improving the weather resistance of rigid PVC moldings, specifically referring to the partial replacement of lead and cadmium with TiO2 by ZnS. Although the improved PVC products have obvious positive effects in terms of weather resistance, the amount of heavy metals in compound PVC products is increasing.

In addition, C-3019632 also describes the role of hydrotalcite in PVC products. Through the structure Mg _1-x Al _x (OH) ₂ A _x/n ^n- .mH ₂ O, it can effectively prevent the degradation of thermoplastic resins to thermal ultraviolet rays . However, it was found that hydrotalcites did not fully achieve the desired effect in terms of stabilizing properties, most importantly their weather resistance.

Other hydrotalcite-type stabilizers, such as [(M ₁ ²⁺ ) _y1 (M ₂ ²⁺ ) _y2 ] _1-x M _x ³⁺ (OH) ₂ A _x/n ^n- in EP-B-189899 .mH ₂ O, in addition to meeting high-quality weather resistance in plastic molding products, other properties cannot meet the requirements of PVC products.

The development of high-efficiency, long-lasting, non-toxic or low-toxic, pollution-free compound multi-function is the general trend of the development of thermoplastic polymer additives in the world. Further develop high-tech products such as additive masterbatch, concentrated additives, compound additives, etc. However, it is also known that the cost of the developed product is relatively high, the variety of multifunctional composite additives is difficult to be widely used, and the production equipment also needs to be complete, and the performance of some pollution-free varieties is still not ideal, such as the known environmentally friendly Ca/Zn thermal There are deficiencies in the stabilizer system, especially when white hard PVC is used outdoors, for example, PVC window profiles, which have an impact on weather resistance, light stability and apparent quality.

Summary of the invention In order to change this situation, the present invention discloses a composite heat stabilizer that can be used for polyvinyl chloride with strong weather resistance, which is a mixture of the following three structural components (A), (B) and (C) , comprising a natural or processed hydrotalcite, a calcium-aluminum-hydroxide-based compound and at least one isocyanate of a polyol or at least one group of hydroxyl groups. Compared with the previous products, it has high-quality and durable weather resistance, does not fade, and has no foam during processing, so it is more suitable for use in outdoor PVC products.

The composite thermal stabilizer of the present invention contains: (100 parts by weight of the composite thermal stabilizer) (A), 1 to 80 parts by weight of natural or processed hydrotalcite, which can arbitrarily improve its surface properties;

The chemical composition of common hydrotalcites includes magnesium-aluminum composite hydroxides, laminated hydroxyl groups, carbonate ions, and crystal water. The special chemical composition and crystal structure make it have a series of unique and excellent properties and functions. For example, in this type of material, the carbonate group can effectively absorb the HCl released during the degradation of PVC, and the use of hydrotalcite at high temperature to lose interlayer water and laminate hydroxyl dehydration can play a role in removing and non-flammability. Layered materials With intercalation properties, it can effectively inhibit the migration of plasticizers and other additives from the polymer matrix to the surface.

(B), 0～70 parts by weight of at least one calcium-aluminum-hydroxide compound, the compound can be selected from:

(1) Calcium-aluminum-hydroxide-phosphite based on general formula (I)

Ca _x Al ₂ (OH) _2(x+3-y) (HPO ₃ ) _y .mH ₂ O (I)

where 2≤x≤12

2x+5/2>y>0 and 0≤m≤12

When 2≤x≤8, y≠1

(2) Calcium-aluminum-hydroxide-carboxylate based on general formula (II)

Ca _x Al ₂ (OH) _[(2x+6)-y] A _y/n ^n- .mH ₂ O (II)

where 2≤x≤12

2x+5/2>y>0 and 0≤m≤12,

1≤n≤8

Among them, A ^-n is an aliphatic saturated or unsaturated, linear or single branched, or polyfunctional anion containing carboxylic acid, containing 1 to 22 carbon atoms; or aromatic, or a single heterocyclic Basic, or polyfunctional anions containing carboxylic acids, containing 6 to 20 carbon atoms and other combinations, when 2≤x≤8, y≠1;

(C), 0-70 parts by weight of at least one polyhydric alcohol or a group of isocyanates of hydroxyl groups.

Its structural formula is as follows:

The composite heat stabilizer for PVC in the present invention can be realized through various physical methods known in the industry, such as pellets, spray particles or particles, flakes or pastilles. The primary products of these products can be made into powder mixtures by kneading and stirring. The pellet products can be formed by pressure and temperature control equipment. The production of shaped particles can be made with the aid of granulation aids, or formed into flakes or ingots by melting and cooling. It can also be atomized to form spray particles. It is added to polyvinyl chloride at a weight ratio of 0.2-6.5% (calculated on the basis of 100 parts by weight of the halogen thermoplastic resin).

In addition, the present invention also discloses advanced derivatives of this type of composite thermal stabilizer, that is, the composite thermal stabilizer obtained above uses low-density polyethylene (LDPE) with a melt index of 0.2-10.0 as a carrier, and other appropriate amount of multifunctional assistants. It is processed into various types of multi-functional compound additive masterbatches through mixing, banburying (kneading), extrusion, granulation and other processes.

The above-mentioned composite heat stabilizer and its derivative auxiliary agent masterbatch, when processing thermoplastic polymers, like PVC, are partly directly added into the molding by simple stirring with resin; partly because of the needs of product functions, fillers or plasticizers are also added Additives, but also repeat the above compound granulation process, after re-granulation, with the known method, molding in the molding cavity.

The advanced derivative auxiliary agent masterbatch material of the described composite heat stabilizer is the total formula (in percent weight ratio), wherein, the addition amount of the above composite heat stabilizer is 1～50%, LDPE (melt index 0.2-10) is added in an amount of 30-70%, and the total amount of other various functional additives is 1-50%. The above components are uniformly mixed by kneading and stirring, and the compound additive masterbatch is formed by the known granulation process mentioned above

In the invention, we known hydrotalcites, for example in DE-A-4425266, EP-A-0189899, DE-A-3843581, U.S.Pat.No.4,883,533, EP-A-0407139, DE-A-4031818, Specifically described in DE-A-4110835, DE-A-4117034, EP-A-0522810, DE-A-4439934, and U.S.Pat.No.5,352,723; and the compound represented by general formula (I), for example in DR- It is described in A-4106411, and the compound represented by general formula (II) is described, for example, in DE-A-4106404.

In addition to the products described above, various functional additives that can be compounded can also be selected from the following 1-12 components.

Some specific active structures and compounds used in the present invention are illustrated below by way of example.

1. The anion A ^n- containing carboxylic acid is included in the general formula (II), and the optional anions include malonic acid, succinic acid, fatty acid, fumaric acid, and maleic acid phthalic acid, isophthalic acid, terephthalic acid, pyridine acid, benzoic acid, salicylic acid, hydroxymalonic acid, malic acid, tartaric acid, acetone dicarboxylic acid of ketonedioic acid, aconitic acid, citric acid and amino acids.

2. The polyol used is a combination of polyols with 2 to 32 carbon atoms and 2 to 12 hydroxyl groups, such as propylene glycol, trishydroxyethyl isocyanurate, glycerol, propylene glycol, neopentyl Glycols, kapokol, xylitol, arabitol, galactitol, iditol, mannitol, sorbitol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol can be use.

3. An optional isocyanate compound containing a hydroxyl group is according to the general formula (III), where the group X and the index n are respectively the same or different, and n is an integer from 0 to 5, more suitable is from 0 to 3, and X can represent a hydrogen atom or a linear or branched alkyl group, with 1 to 6 carbon atoms, more suitably 1 or 2 carbon atoms, where at least n is not A function equal to 0 is more appropriate, and all X and n have the same meaning.

4. Suitable organotin salts that may be used are methyl-, butyl-, or octyltin carboxylates, half-esterified maleic anhydride or mercaptan salts.

5. Suitable divalent metal salts of carboxylic acids include barium, cadmium, zinc, calcium, magnesium, or (preferably) saturated or unsaturated fatty acids or aromatic salts. In the case of zinc, basic (basic) salts may optionally be employed. Barium and calcium salts of phenolic acid or substitute phenolic acid, and alternatively essentially carbonates, phenolates, carboxylates. A combination of metal salts in the compound is very suitable, like barium-cadmium salt, barium-zinc salt or calcium-zinc salt. Suitable salts include acetate, ethyl n-hexanoate, caprylate, stearate, oleate, laurate, palmitate, myristate, ricinoleate, benzoate, Phthalates, phenolates and nonyl phenolate. Alternatively these divalent metal salts may be used in combination with salts of monovalent metals containing carboxyl groups, such as sodium, potassium, or trivalent metals, such as aluminum. In addition, inorganic metal salts may be included, such products may be oxides, carbonates, perchlorates, sulfates, magnesium/aluminum and magnesium/aluminum/zinc hydroxycarbonates, calcium/aluminum Hydroxycarbonate, calcium/aluminum hydroxyphosphite products.

6. Optional plasticizers: phthalic acids, such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, butyl octyl phthalate, o-phthalate Dicyclohexyl dicarboxylate, etc.; plasticizers with auxiliary stabilizing effects, organic phosphites, such as triaryl phosphite, like triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2 , 4-di-tert-butylphenyl) phosphite; another example is alkyl aryl phosphite, like biphenyl monooctyl phosphite, phenyl dioctyl phosphite; mixed alkylnonylphenyl phosphite esters, trialkyl phosphites like tridecyl phosphite, trioleyl phosphate, tristearate phosphite; those based on pentaerythritol, dipropylene glycol and bisphenol A like oligosaccharide phosphite.

7. Antioxidants: such as phenolic antioxidants, such as 2,6-di-tert-butyl-4-phenol, styrene phenol, 2,2'-methylene-bis(4-methyl-6-tert-butyl phenol), 2,2'-bis-(4-resorcinol) propane, octadecyl-3-(3',5'-di-tert-butyl-4-resorcinol) acrylate, Pentaerythritol-tetrakis-[3',5'-di-tert-butyl-4-resorcinol] acrylate], etc.

8. Ultraviolet absorbers: such as benzophenone, like 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octadecylmethoxybenzophenone; benzotriazole, like 2-(2 -Hydroxy-5-methylphenyl)benzotriazole; Salicylates, like phenyl salicylate; Nickel salts, like nickel-bis-(octylphenyl sulfide) and nickel-bis[0 -Ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)]phosphate, amines hinder absorbers like di-(2,2,6,6-tetramethyl-4-piperidine) Sebacate.

9. Antistatic agent: such as ethylene concentrate, polyethylene glycol, glycerol monostearate, hydroxysulfonate.

10. Lubricants: calcium stearate, zinc stearate, fatty acid esters and amino compounds, glyceryl phthalate distearate, stearyl alcohol, octadecyl fatty acid, paraffin wax, polyethylene wax, amides wax etc.

11. Flame retardants: like antimony trioxide, magnesium hydroxide, aluminum hydroxide, zinc stannate.

12. Impact modifier: for example: chlorinated polyvinyl, butadiene/styrene copolymer or butadiene/styrene/propylene terpolymer. Acrylic impact modifiers and processes are also covered.

Stabilizing aids according to the invention can also be added together, like fillers (eg chalk, kaolinite), pigments (eg titanium dioxide, zinc sulfide), reinforcing aids (eg glass fiber, talc) and the like.

The masterbatch formed by the composite heat stabilization additive and its advanced derivatives of the present invention is mainly used in polyvinyl chloride molded products. Compared with the prior art, the present invention has the following obvious beneficial effects:

1. PVC products have excellent light resistance and long-lasting weather resistance. After testing, using the invented composite heat stabilizer product, it has basically no color difference from the original color after three years of outdoor weather exposure.

2. When the thermoplastic polymer is processed and molded, the foaming property is effectively reduced to a minimum.

3. It has good compatibility with thermoplastic polymers and their additives, and can further manufacture high-tech products such as auxiliary agent masterbatch, concentrated auxiliary agent, and compound auxiliary agent.

4. The compound additive improves the traditional production process, saves labor links, greatly improves production efficiency, and saves resources and costs.

5. The source of raw materials is abundant, there is no dust in the molding process, and it is non-toxic or low-toxic, which is in line with the development trend of environmental protection.

Detailed ways:

The present invention is described by way of Example 1 and Example 2 below.

In the table, X is a non-invention component; Y is an invention component. In the example, the extruded pvc slides were precisely measured for their weather resistance and light stability according to the DIN 6167 standard (D65/10 type light exposure) as a function of simulated exposure to air. The following accurately records the PVC cross-sections through the following treatment process to evaluate their weather resistance.

The above components are mixed with pvc, through a stirring mixer with heating/cooling function, first heated to 120 degrees, and then cooled to 40 degrees. After dry mixing, it was extruded by an extruder to obtain a cross-section carrier sheet for experiments.

The extruded slide obtained by the method described above was cut into a size of 1.5×1.5 cm, and exposed to natural weather conditions. After 4 months, the sample was removed from the weathering test system, and the color value of the finalized sample was tested. Yellow value (b-value) of the samples, measured after a weathering period according to DIN 6167 (lighting type D 65/170).

A sample of the melt extruded support sheet was also evaluated for its strong foaming properties. Now prepared according to the above-mentioned process method, the extruded molding material of the sol that has been heat-treated at 200 degrees has been prepared. The material is subjected to such a thermal load, on the one hand to observe the coloring properties, and on the other hand to pay attention to the formation of gradually increasing foam, which is mainly caused by _CO2 and crystallization water in the hydrotalcite. After 25 minutes of molding, the foaming performance was determined by observing the amount of foam on a square slide.

Judgment: It is mainly to judge the size of the bubble.

Foams with a diameter size of 1 mm are classified as "small" and foams greater than or equal to 3 mm are "large". According to this standard, different stabilizers, such as different types of hydrotalcites, can be judged well.

In the stability test, the HCI value is in accordance with DIN VDE 0472 part 614 (Congo red test).

Illustrate the action characteristic of the present invention in component by example 1 and example 2 below:

Example 1 (formed into components X and Y according to the example) X1 X2 X3 X4 Y1 Y2 Y3 Y4 Y5 S-pvcK-value 68 Impact Modifier ¹⁾ Chalk TiO ₂ Phthalate Glyceryl Distearate Bisphenol A Paraffin Benzyl Stearyl Methane Pyruvate Calcium Acetate Ca ₄ Al ₂ (OH) ₁₂ HPO _3.3H2O Hydrotalcite ²⁾ Polyol Stabilizer ³⁾ Zinc Stearate   1007540.60.20.20.20.2--1.00.20.8 1007540.60.20.20.20.2--1.0--0.8 1007540.60.20.20.20.20.10.9--0.8 1007540.60.20.20.20.21.0--0.20.8 1007540.60.20.20.20.20.10.90.20.8 1007540.60.20.20.20.20.20.80.20.8 1007540.60.20.20.20.20.30.70.20.8 1007540.60.20.20.20.20.40.60.20.8 1007540.60.20.20.20.20.50.50.20.8

1) BA/MMA graft copolymer

2) Haichuan HCH-508 (trade name)

3) Tris-(2-hydroxyethyl)isocyanurate

Table 1 shows the yellowness values (b-values) tested at weathering time.

Table 1

Example 1 yellow value number of months 0 4 8 12 16 20 twenty four 28 32 b-value X1 3.6 4.9 6.5 8.3 9.6 9.9 9.2 8.1 7.4 b-value X2 4.2 5.3 7.4 9.9 11.3 12.7 14.2 12.4 11.6

b-value X3 4.0 5.3 5.9 7.6 10.3 10.5 9.7 9.6 8.5 b-value X4 2.7 3.5 5.3 6.2 7.6 8.9 8.7 7.4 7.4 b-value Y1 3.4 3.8 4.3 5.8 6.3 6.9 7.9 6.3 6.0 b-value Y2 3.3 3.6 4.0 5.1 6.8 6.7 5.7 5.2 4.9 b-value Y3 3.0 3.6 3.9 4.7 5.4 6.3 6.1 5.7 5.1 b-value Y4 2.8 3.2 3.9 4.9 5.8 7.1 6.2 6.9 5.3 b-value Y5 2.7 3.6 3.7 5.6 5.3 6.4 7.2 6.3 5.7

Table 2

Example 1 foam quantity, type and HCl value X1 X2 X3 X4 Y1 Y2 Y3 Y4 Y5 foam quantity 6 27 twenty four none twenty three 20 14 12 8 type big big Small none Small Small Small Small Small HCl value 35 32 33 26 36 36 34 34 33

As can be seen from Table 1, the initial color of Example Y1 is greatly improved over the non-inventive Examples X1-X3. The more Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ O is added, the more the yellow value of the molded product decreases. It can be inferred from Table 2 that the increase in the number of applications did not lead to a decrease in stability.

In the natural weather environment, the yellow value of the invention example Y1-Y5 is compared with the example X1-X4, and the yellow value is uniformly and gradually increased. Comparing examples Y1-Y5, examples X1-X4 show a clear increase in growth rate. In the case of weather exposure, this rising yellow value was significantly reduced after adding the contrast 10% Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ O hydrotalcite stabilizer. After 16 months, which is half the weathering time, the invented example compared to the non-invented, visually shows only a minor change in color.

Blister performance was measured by a 25 minute extruded square sol slide as described above. Judging from Table 2, it is known that the foaming tendency decreases with the gradual increase of Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ O. It is clearly shown on the sample carrier that the foam is reduced and smaller, which means that in the pvc molding process, the present invention will bring a leap forward and positive progress.

Example 2 (form into components X and Y according to the example)

Y6 Y7 Y8 X5 Y9 Y10 S-pvcK-value 68 Impact Modifier ¹⁾ Chalk TiO ₂ Glyceryl Distearate Phthalate Bisphenol A Paraffin Benzyl Stearyl Methane Calcium Acetylacetonate Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ OCa ₄ Al ₂ (OH) ₁₃ HPO ₃ .(Fumarate) 3H ₂ O Hydrotalcite ²⁾ Polyol Stabilizer ³⁾ Polyol TMP ⁴⁾ Zinc Stearate 1007540.60.20.20.20.2--0.10.90.2--0.8 1007540.60.20.20.20.2--0.30.70.2--0.8 1007540.60.20.20.20.20.150.150.70.2--0.8 1007540.60.20.20.20.2----1.0--0.20.8 1007540.60.20.20.20.20.2--0.80.20.8 1007540.60.20.20.20.20.10.10.8--0.20.8

1) BA/MMA graft copolymer

2) HCH-508 (trade name)

3) Tris-(2-hydroxyethyl)isocyanurate

4) Trimethylolpropane

Table 3 shows the yellowness values (b-values) tested at weathering time.

Example 2 yellow value number of months 0 4 8 12 16 20 twenty four 28 32 b-value Y6b-value Y7b-value Y8 3.32.83.0 4.14.13.8 4.55.44.0 6.46.25.1 6.67.16.8 7.28.07.6 7.76.57.0 5.95.75.4 6.35.55.9

b-value X5 3.6 5.4 7.0 8.1 10.7 9.2 9.1 8.3 6.3 b-value Y9 3.3 4.1 5.2 6.3 6.7 7.1 5.4 6.0 5.8 b-value Y10 3.1 3.6 4.3 5.1 6.8 6.7 5.7 5.2 4.6

Table 4

Example 2 Foam quantity, type and HCl value Y6 Y7 Y8 X5 Y9 Y10 foam quantity 19 6 8 33 19 twenty three foam type Small Small Small big Small Small HCl value 37 35 35 34 34 34

When the calcium/aluminum/hydroxide carboxylate and the calcium/aluminum/hydroxide phosphite are combined together, Y6-Y8 in the example shows a benign synergistic effect. The original color has been improved compared to X1 or X5. After weathering exposure, the rate of rise in the yellow value of Comparative Examples Y1-Y4 Examples X6-X8 was very low. Furthermore, the TMP used in Examples Y9 and Y10 is a further polyol compared to Examples X5 and X3. It is particularly evident here that, in combination with Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .(fumarate) 3H ₂ O or Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ O and hydrotalcite, it exhibits very good Excellent weather resistance and reduced blistering.

The following specific formula examples 3-example 4, based on the component (I), (II), (III) composite heat stabilizer of the structural invention, according to the difference of purposes, add other functional additives and LDPE (melt index 0.2- 10) Mixing, through the known granulation process, processed into multifunctional compound additive masterbatch:

Example 3 is applied to the formulation of stabilizer advanced derivative masterbatch of white outdoor PVC profiles

LDPE (BASF 1810E) 30-70 Impact modifier BA/MMA graft copolymer 0-45 Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ O 1-30 Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .(fumarate) 3H ₂ O 1-30 Amide wax 0.5-5

2-Hydroxy-4-methoxybenzophenone 0.5-5 Glyceryl Distearate Phthalate 0.5-10 Bisphenol A 0.5-5 Benzyl stearyl methane 0.5-5 calcium acetylacetonate 0.5-5 Hydrotalcite (HCH-508 from Haichuan Company) 1-20 Tris-(2-hydroxyethyl)isocyanurate 0.5-5 Zinc stearate 0.5-10

Example 4 is applied to the formula of heat stabilizer advanced derivative masterbatch of PVC translucent packaging film

LDPE (BASF 6001L) 30-70 Ca ₄ Al ₂ (OH) ₁₂ HPO ₃ .3H ₂ O 1-30 Polyethylene wax 0.5-5 2-Hydroxy-4-methoxybenzophenone 0.5-6 Glyceryl Distearate Phthalate 0.5-10 Bisphenol A 0.5-5 Benzyl stearyl methane 0.5-5 calcium acetylacetonate 0.5-5 Trimethylolpropane 0.5-5 Zinc stearate 0.5-10 Epoxidized soybean oil 5-50 Processing aids 2-10 Hydrotalcite (Shenzhen Haichuan Company HCH-508) 0.5-10

Claims (4)

1, a kind of polyvinyl-chloride use composite thermal stabilizer, the composition for following (A), (B), (C) three kinds of structural constituents when composite thermal stabilizer is benchmark with 12 weight parts, consists of:

(A), the hydrotalcite crossed of 5～9 parts nature or processing treatment;

(B), at least a calcium-aluminium-compound hydroxy of 1～5 part, this compound can be selected from:

(1) based on calcium-aluminium-hydroxide radical-phosphite of general formula (I)

Ca _xAl ₂(OH) _2(x+3-y)(HPO ₃) _y·mH ₂O (I)

2≤x≤12 wherein

2x+5/2＞y＞0 and 0≤m≤12

When 2≤x≤8, y ≠ 1

(2) based on calcium-aluminium-hydroxide radical-carboxylate salt of general formula (II)

Ca _xAl ₂(OH) _[(2x+6)-y]A _y/n ^n-·mH ₂O (II)

2≤x≤12 wherein

2x+5/2＞y＞0 and 0≤m≤12

1≤n≤8

Wherein, A ^-nBe aliphatic saturated or undersaturated a, straight chain or single branched, or the polyfunctional anion of carboxylic acid that contains, 1～22 carbon atom contained; Or aromatic base or single heterocyclic radical or the polyfunctional anion of carboxylic acid that contains, contain 6～20 carbon atoms combinations, when 2≤x≤8, y ≠ 1;

(C), at least one polyvalent alcohol of 2 parts or the isocyanate of one group of hydroxy, its structural formula is as follows:

Here, n is an integer, from 0 to 5, and X can show a hydrogen atom or a straight chain or have the alkyl of side chain, and 1 to 6 carbon atom is arranged.

2, composite thermal stabilizer according to claim 1 is characterized in that, is included in the general formula (II) to contain anion of carboxylic acid A ^N-For: propanedioic acid, Succinic Acid, lipid acid, fumaric, maleic acid, phthalic acid, m-phthalic acid, terephthalic acid, pyridine acid, M-nitro benzoic acid, salcylic acid, equisetic acid, citric acid with amino acid whose.

3, composite thermal stabilizer according to claim 1 is characterized in that, the polyvalent alcohol of use has the polyvalent alcohol combination of 2～32 carbon atoms and 2～12 hydroxys.

4, composite thermal stabilizer according to claim 1 is characterized in that, it is added in the polyvinyl chloride, calculates with the thermoplastic resin weight 100% of halogen, and weight ratio is 0.2～6.5%.