CN1536015A - Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition - Google Patents
Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition Download PDFInfo
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Abstract
The present invention relates to a composite thermo-stabilizer for thermoplastic polymer containing haloid element, specially it is a thermo-stabilizer and its derivative composite for PVC. Said thermo-stabilizer contains 1-80 weight portions of one natural or processed hydrotalcite, 0-70 weight portions of one compound based on calcium-aluminium-hydroxide radical and at least one polybasic alcohol and 0-70 weight portions of at least one group of isocyanates based on hydroxide group. Said thermo-stabilizer is mixed with LDPE (low density polyethylene) and some PVC functional adjuvants so as to form the invented high-grade derivative composite of said composite stabilizer, in which the added quantity of stabilizer is 1-50%, added quantity of LDPE is 30-70% and total added quantity of other several functional adjuvants is 1-50%. Said invention can be used for making PVC products.
Description
Technical field the present invention relates to a kind of used thermo-stabilizer and derivative composition thereof of composite thermal stabilizer, particularly polyvinyl chloride that is used to contain the thermoplastic polymer of halogen element.
Background technology is along with the continuous growth of thermoplastic polymer output, and the consumption of its processing aid also increases thereupon.Thermo-stabilizer is mainly used in the processing of polyvinyl chloride (PVC) goods as one of important classification wherein, since prevent that goods in use are heated, the destruction of oxygen and water, thereby prolong work-ing life of goods.
The known polymkeric substance that contains halogen is subject to ultraviolet ray, the influence of light and heat and decomposition reaction takes place, thus destroy its service performance.Resemble polyvinyl chloride especially, easily penetrate, heat in the extrusion moulding process and have under the situation of water and decompose at light, and so decomposition can make that the product mechanical property is aging, coating decomposition etc.For fear of the polymeric decomposition reaction of PVC, just must make the stablizer that is adopted to act on the plasticity polymer for a long time.At present, the thermo-stabilizer that polyvinyl chloride is commonly used can be divided into lead salts, metallic soap class, organic tin, antimony organic, liquid composite stabilizing agent and other auxiliary stabilizer etc.
The lead salts stablizer is the thermo-stabilizer that the PVC goods use the earliest, still uses in a large number now, and cost is low, have good thermostability (can also absorb ultraviolet ray under some situation), particularly long-term thermal stability is good, and electrical insulating property is good, performance with white pigment, sticking power is big, and weathering resistance is good, but is not suitable for being used in the occasion that requires not have sulphur pollution, and not anti-sulfuration, have toxicity, consistency and dispersiveness are slightly poor, and resulting product is opaque.
Organotin also is highly effective thermo-stabilizer, can make transparent article keep very high transparency and consumption minimum, most of organotin is poisonous, but some organo-tin het stabilizer based on the dioctyl tin compound still allow as with the stablizer of Food Contact product because their toxicity is lower and anti-dissolubility is fine.Thiol organotin is the dialkyl group thiol organotin particularly, is that stabilising effect is best in the existing thermo-stabilizer, and it is applicable to all types and other PVC of level, but, cost is than higher, and thiol organotin is incompatible with the lead salt stable product, and both mixing can cause the blackening of material color.
Metal soap thermal stabilizers uses with multiple metallic soap compound form usually, and composition metal stablizer commonly used is Ba/Cd and Ba/Cd/Zn stabilising system.The existing liquid product of this stable system also has solid product, and their main drawback is that stabilising effect is different because of the kind of PVC, precipitate easily in the course of processing, and to the sulphur pollution sensitivity, these then can not take place in containing the Zn system.
Although at present thermo-stabilizer production and the exploitation of China obtain pretty good achievement, compare with advanced international standard and still have many deficiencies and gap greatly.(1) kind is few, unreasonable structure, and the lead salts stabilizer comprises of high poison, high pollution, low grade is according to absolute dominant position, and the organic tin proportion is well below the level of developed countries; (2) industrial scale is little, poor product quality; (3) exploitation dynamics is not enough, and the funds of input are very few; (4) the loaded down with trivial details backwardness of production technique, the duplication of labour, cost strengthens.
As a big kind of general plastic, the output of polyvinyl chloride (PVC) is sure to occupy the prostatitis always in polymer industry, and the development of thermo-stabilizer is closely related with the PVC industrial expansion with production.And under the requirement of international overall situation and environmental legislation, current PVC thermo-stabilizer just develops towards low toxicity-nontoxic and compound direction, seeks a kind of novel thermo-stabilizer and substitutes stablizer poisonous, dust pollution and become the certainty of era development.
EP-B-424572 discloses a kind of modification method of weathering resistance of hard PVC forming composition, specifically is meant by ZnS partly to replace lead and cadmium with TiO2.Though through the PVC goods after the improvement tangible positive effect has been arranged aspect weathering resistance, the heavy metal amount that forms in the Compound P VC goods is to be growing on and on.
In addition, C-3019632 has also described the effect of hydrotalcite in the PVC goods, by structure Mg
1-xAl
x(OH)
2A
X/n N-.mH
2O can effectively stop thermoplastic resin for the ultraviolet degraded of heat.Yet find that hydrotalcite does not obtain desired effect fully on stabilising characteristic, most important is their weathering resistance.
The stablizer of other hydrotalcite type is as the [(M among the EP-B-189899
1 2+)
Y1(M
2 2+)
Y2]
1-xM
x 3+(OH)
2A
X/n N-.mH
2O, except satisfying high-quality weather resistance, other performance can't satisfy the PVC product requirements in the plastic shaping goods.
Exploitation is efficient, hold effects, the composite multifunction of nontoxic or low toxicity, nuisancelessization is the general trend that global thermoplastic polymer auxiliary agent develops.Further develop the product that aid master batches, concentrated assistant, composite assistant etc. have high-tech content.But also know, the development product cost is than higher, the single widespread usage that is difficult to of multi-functional composite assistant kind, production unit also needs comprehensive, the varieties and characteristics of some nuisancelessization still is not ideal enough, and resembling known environment-friendly type Ca/Zn heat stabilizer system just has weak point, particularly Bai Se the hard pvc of use out of doors, pvc window sectional material for instance, influential just have weathering resistance, light stability and an apparent mass etc.
Summary of the invention is in order to change this present situation, the invention discloses the very strong composite thermal stabilizer that can be used for polyvinyl chloride of a kind of weathering resistance, mixture for following (A), (B), (C) three kinds of structural constituents, wherein comprised a kind of hydrotalcite natural or that processing treatment is crossed, a kind of isocyanate based on calcium-aluminium-compound hydroxy and at least one polyvalent alcohol or at least one group of hydroxy.Use it for the processing of PVC goods, compared with former goods and have high-quality persistent weathering resistance, do not fade, and add and do not steep the end man-hour, preferably being used in the outdoor PVC goods.
This composite thermal stabilizer of the present invention contains: (is 100 weight parts with composite thermal stabilizer)
(A), the nature of 1～80 weight part or the hydrotalcite that processing treatment is crossed, can improve its surface property arbitrarily;
The chemical constitution of common hydrotalcite comprises magnalium complex hydroxide, laminate hydroxyl, carbanion and crystal water.Special chemical constitution and crystalline structure make it have the performance and the function of a series of uniquenesses, excellence.For example, in such material, the HCl that deviates from when carbonate can absorb the PVC degraded effectively, utilize and lose middle water and the dehydration of laminate hydroxyl under the hydrotalcite high temperature, can play going and not having a fire-retardant effect, stratified material has the intercalation characteristic, can suppress effectively softening agent and other additives from polymeric matrix to surface transport.
(B), at least a calcium-aluminium-compound hydroxy of 0～70 weight 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
-aBe 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 or the like combinations, when 2≤x≤8, y ≠ 1;
(C), the isocyanate of at least one polyvalent alcohol of 0～70 weight part or one group of hydroxy.
Its structural formula is as follows:
The composite thermal stabilizer of PVC of the present invention can be achieved by multiple industrial known physics mode, as being bead, spraying granule or particulate, thin slice or ingot sheet.These products are elementary can be made into the powdery mixture by mediating to stir; the bead product can be by pressure and Temperature-controlled appliance technological forming; shaped granule production can be by means of granulating assistant, or forms thin slice or ingot sheet by the fusing cooling, and the formation spraying granule also can atomize.It is added in the polyvinyl chloride, and weight ratio is 0.2-6.5% (with 100 parts of calculating of thermoplastic resin weight of halogen).
In addition, the invention also discloses the higher derivative of this type of composite thermal stabilizer, the new LDPE (film grade) (LDPE) that is about to above-mentioned gained composite thermal stabilizer and with the melting index is 0.2-10.0 is a carrier, be mixed with other an amount of multifunctional assistant combination, by mixing, banburying (kneading), extrude, technology such as granulation, be processed into various types of other and have multi-functional composite assistant master batch material.
Above-mentioned composite thermal stabilizer and derivative auxiliary agent master batch material thereof add man-hour at thermoplastic polymer, resemble PVC, and part is by directly adding moulding with the resin simple agitation; Part also will repeat top composite granulation process flow process because the needs of product function also will add additives such as filler or softening agent, after granulation once more, in a known manner, moulding in the chamber is touched in moulding.
The higher derivative auxiliary agent master batch material of described this composite thermal stabilizer is total prescription (for percent by weight), wherein, the addition of above-mentioned composite thermal stabilizer is 1～50%, the addition of LDPE (melting index 0.2-10) is 30～70%, and the total addition level of other multiple functional aids is 1～50%.Above component by the kneading mixing that stirs, is formed the composite assistant master batch material by known granulation process recited above
In invention, our known hydrotalcite is for example at DE-A-4425266, EP-A-0189899, DE-A-3843581, U.S.Pat.No.4,883,533, EP-A-0407139, DE-A-4031818, DE-A-4110835, DE-A-4117034, EP-A-0522810, DE-A-4439934, and U.S.Pat.No.5, specific descriptions are arranged in 352,723; And the compound of general formula (I) performance for example has description in DR-A-4106411, and the compound of general formula (II) performance for example has description in DE-A-4106404.
Except product described above, multiple functional aid that can be composite also can be selected from following 1～12 component.
Below by illustrating the concrete active structure of the used part of the present invention, compound.
1, contains anion of carboxylic acid A
N-Be included in the general formula (II) the selectable anionic propanedioic acid that has, Succinic Acid, lipid acid, fumaric, maleic acid, phthalic acid, m-phthalic acid, terephthalic acid, pyridine acid, M-nitro benzoic acid, salcylic acid, tartronic acid, oxysuccinic acid, tartaric, Bing Tongersuosuan, oxosuccinic acid, equisetic acid, citric acid with amino acid whose.
2, the polyvalent alcohol of Shi Yonging has the polyvalent alcohol combination of 2～32 carbon atoms and 2～12 hydroxys, resembles propylene glycol, tris(2-hydroxy ethyl)isocyanurate, glycerol, propyleneglycoles, neopentyl glycol, kapok alcohol, Xylitol, arabitol, melampyrum, iditol, N.F,USP MANNITOL, Sorbitol Powder, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol and tripentaerythritol all can be used.
3, the selectable isocyanate compound of hydroxy that contains is according to general formula (III), radicals X is the same or different with index n respectively there, and n is an integer, from 0 to 5, preferably is from 0 to 3, and X can show a hydrogen atom or a straight chain or have the alkyl of side chain, 1 to 6 carbon atom is arranged, preferably is 1 or 2 carbon atom, be at least here n to be not equal to 0 function be preferably, all X and n have same implication.
4, suitable organic tin salt may by usefulness have methyl-, butyl-, or tin octylate carboxylate salt, the MALEIC ANHYDRIDE of half esterization or thiol group salt.
5, the metal-salt of Shi Yi carboxylic acid divalence has barium, cadmium, and zinc, calcium, magnesium, or (suitable) the saturated or unsaturated aliphatic or aromatic acid salt of guiding.In the situation of zinc, basic (alkalescence) salt can selectively be adopted.Carbolic barium salt and calcium salt or replacement phenylic acid, and selectively be carbonate, phenolate, carboxylate salt substantially.The combination of metal-salt is very suitable in composite, as barium-cadmium salt, in barium-zinc salt or the calcium-zinc salt.Suitable salt comprises acetate, ethyl group n-hexoate, octylate, stearate, oleate, lauroleate, palmitate, myristate, ricinate, benzoate, phthalate, phenolate and nonyl phenolate.The metal-salt of selectable these divalence may be used to combination, for example sodium, potassium, or tervalent metal, for example aluminium with the hydrochlorate that monovalent metal contains carboxyl.In addition, in inorganic metal-salt may be included in, such product may be an oxide compound, carbonate, perchlorate, vitriol, the hydroxyl carbonate of magnesium/aluminium and magnesium/aluminium/zinc, the hydroxyl carbonate of calcium/aluminium, the hydroxyl phosphite product of calcium/aluminium.
6, selectable softening agent: the O-phthalic acids resembles dimethyl phthalate, diethyl phthalate, dipropyl phthalate, butyl octyl phthalate, dicyclohexyl phthalate etc.; Softening agent with auxiliary stabilization, organic phosphorous acid ester, tricresyl phosphite aromatic ester for example, as triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, three (2,4-two-tert-butyl-phenyl) phosphorous acid ester; Phosphorous acid alkane aromatic ester and for example is as phosphorous acid biphenyl one monooctyl ester, phenyl dioctyl phosphite; Blended phosphorous acid alkyl nonyl phenylester, tricresyl phosphite alkane ester is as phosphorous acid tridecane ester, trioleyl phosphate, tricresyl phosphite stearate; Based on tetramethylolmethane, dipropylene glycol and dihydroxyphenyl propane, as the few candy ester of phosphorous acid.
7, antioxidant: phenol antioxidant for example, resemble 2,6-two-tertiary butyl-4-phenol, styrenated phenol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 2,2 '-two-(4-resorcinol) propane, octadecyl-3-(3 ', 5 '-di-t-butyl-4-resorcinol) acrylate, tetramethylolmethane-four-[3 ', 5 '-di-t-butyl-4-resorcinol] acrylate] etc.
8, UV light absorber: benzophenone for example resembles 2-hydroxyl-4-anisole ketone, 2-hydroxyl-4-18 anisole ketones; Benzotriazole resembles 2-(2-hydroxy-5-methyl base phenyl) benzotriazole; Salicylate resembles phenylsalicylic acid salt; Nickel salt resembles nickel-two-(octyl phenyl sulfide) and nickel-two [O-ethyl group (3, the 5-di-tert-butyl-4-hydroxyl benzyl)] phosphoric acid salt, and amine hinders absorption agent, resembles two-(2,2,6,6-tetramethyl--4-piperidines) sebacates.
9, static inhibitor: ethene enriched material for example, polyoxyethylene glycol, monostearate glycerine, hydroxy sulfonate.
10, lubricant: as calcium stearate, Zinic stearas, fatty acid ester and aminocompound, O-phthalic acid glycerol two hard ester acid esters, Stearyl alcohol, 18 lipid acid, paraffin, Ployethylene Wax, acid amides is cured etc.
11, fire retardant: as ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide, aluminium hydroxide, zinc.
12, impact modifier: for example: chlorination polyethylene, the rare terpolymer of Butadiene co-polymer or Butadiene/third.In the impact modifier of acrylic acid or the like and technology also are included in.
Stabilization aid according to invention can also add together, as stopping composition (as chalk, kaolinite), and pigment (as titanium dioxide, zinc sulphide), reinforcing aids (as glass fibre, talcum) etc.
Compound thermally-stabilised auxiliary agent of the present invention and the formed master batch of higher derivative thereof are mainly used in the polyvinyl chloride moulding product, and compared with prior art, the present invention has following tangible beneficial effect:
1, the PVC goods have good photostabilization and persistent weathering resistance.After tested, use the composite thermal stabilizer product of invention, during weather out of doors exposes for 3 years, with the basic no color differnece of priming color.
2, thermoplastic polymer is when machine-shaping, and whipability is effectively reduced minimum.
3, good with thermoplastic polymer and additive compatibility thereof, can further make high-tech content products such as aid master batches, concentrated assistant, composite assistant.
4, composite assistant has improved traditional processing technology, has saved the work link, has greatly improved production efficiency, economizes on resources and cost.
5, raw material sources are abundant, do not have dust in the moulding process, and nontoxic or low toxicity meets the environmental protection development trend.
Embodiment:
Below by describing the present invention in example 1 and the example 2.
Be non-invention component by X in the table; Y is the invention component.In example, the pvc slide glass of extruding formation by exposing airborne function in simulation, has been measured its weathering resistance and light stability according to DIN 6167 standards (the D65/10 type light is shone) accurately.Thereby write down the PVC cross section below accurately and assessed their weathering resistance by following treatment process.
Said components is mixed good with pvc, by a stirring mixer, be heated to 120 degree earlier with heating/refrigerating function, be cooled to 40 degree then.After dried mixing, extrude acquisition experiment cross section slide glass by forcing machine.
The slide glass of extruding that the method that will describe through the top obtains is cut into 1.5 * 1.5cm size, and is exposed under the natural weather situation, and after 4 months, sample shifts out from the weathering test macro, the colour of the sample that test has been finalized the design.The yellow value of sample (b-value) is measured according to DIN 6167 (D 65/170 type light is shone) at the weathering after date.
The slide glass sample that melt extrudes is also assessed its strong performance of bubbling.Now prepared, spent the one-tenth section bar of colloidal sol that heat treated are crossed through squeezing out by 200 according to above-mentioned processing method.Material is on the one hand observed tinctorial property under such thermal load, and will note the formation at the bubble end that increases gradually on the other hand, and the reason that the bubble end forms mainly is the CO in the hydrotalcite
2And crystal water.After through moulding in 25 minutes,, measure foaming intensive performance by observing the bubble end quantity of a square slide glass.
Judge: mainly be to pass judgment on the foamy size.
The foam of 1 mm dia size classifies as " little ", is " big " more than or equal to 3 millimeters foams.According to this standard, different stablizers is arranged, as with dissimilar hydrotalcites, can both judge well.
In the steady testing, the HCI value is according to DIN VDE 0472 part 614 (Congo red test).
The action characteristic in component below by example 1 and example 2 explanation the present invention:
Example 1 (press example and be made into component X and Y)
X1 X2 X3 X4 Y1 Y2 Y3 Y4 Y5
S-pvc 100?100?100?100?100?100?100?100?100
K-value 68
Impact modifying agent
1)777777777
Chalk 555555555
TiO
2 4 4 4 4 4 4 4 4 4
Phthalic acid Stearic diglyceride 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
Dihydroxyphenyl propane 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Paraffin 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Phenmethyl stearyl methane 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Pyruvic acid calcium acetate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Ca
4Al
2(OH)
12HPO
3.3H2O — — 0.1?1.0?0.1?0.2?0.3?0.4?0.5
Hydrotalcite
2)1.0 1.0 0.9-0.9 0.8 0.7 0.6 0.5
Polyol stabilizer
3)0.2---0.2 0.2 0.2 0.2 0.2 0.2
Zinic stearas 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
1) BA/MMA graft copolymer
2) Haichuan Company HCH-508 (trade(brand)name)
3) three-(2-hydroxyethyl) isocyanuric acid esters
Table 1 has shown the yellow value (b-value) at the weathering time test.
Table 1
Example 1 yellow value
The moon several 048 12 16 20 24 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 bubble amt, type and HCl value
X1 X2 X3 X4 Y1 Y2 Y3 Y4 Y5
Bubble amt 6 27 24 does not have 23 20 14 12 8
The type size is no slight slight
HCl value 35 32 33 26 36 36 34 34 33
Can see that by table 1 the routine X1-X3 that priming color contrasts non-invention among the routine Y1 is significantly improved.Ca
4Al
2(OH)
12HPO
3.3H
2It is many more that O adds, and the yellow value of moulding product reduces many more.Can infer that from table 2 increase of number of applications does not cause the reduction of stability.
In the weather environment of nature, the example Y1-Y5 of invention and the example of X1-X4 relatively, yellow value be evenly increase gradually.Comparative example Y1-Y5, example X1-X4 show that tangible speedup rises.Under the situation that weather exposes, the yellow value of this rising is at the Ca that adds contrast 10%
4Al
2(OH)
12HPO
3.3H
2Behind the O hydrotalcite stablizer, obviously reduce.After 16 months, be exactly the weathering time of half, the example of invention contrasts non-invention, and Show Color has only less variation very intuitively.
According to the description of top, weigh lathering property and test by a square colloidal sol slide glass of extruding in 25 minutes.Judgement table 2 knows that foaming trend is along with increasing Ca gradually
4Al
2(OH)
12HPO
3.3H
2O and reducing reduces.Show very clearly that on specimen slides foam is reduced and diminishes, this just means that also in the pvc forming process, the present invention can bring the positive progress of leap.
Example 2 (press example and be made into component X and Y)
Y6 Y7 Y8 X5 Y9 Y10
S-pvc 100 100 100 100 100 100
K-value 68
Impact modifying agent
1)777777
Chalk 555555
TiO
2 4 4 4 4 4 4
Glycerine two hard ester acid phthalates 0.6 0.6 0.6 0.6 0.6 0.6
Dihydroxyphenyl propane 0.2 0.2 0.2 0.2 0.2 0.2
Paraffin 0.2 0.2 0.2 0.2 0.2 0.2
Phenmethyl stearyl methane 0.2 0.2 0.2 0.2 0.2 0.2
Acetylacetonate calcium 0.2 0.2 0.2 0.2 0.2 0.2
Ca
4Al
2(OH)
12HPO
3.3H
2O — — 0.15?— 0.2 0.1
Ca
4Al
2(OH)
12HPO
3. (fumaric acid esters) 3H
2O 0.1 0.3 0.15---and 0.1
Hydrotalcite
2)0.9 0.7 0.7 1.0 0.8 0.8
Polyol stabilizer
3)0.2 0.2 0.2---
Polyvalent alcohol TMP
4)---0.2 0.2 0.2
Zinic stearas 0.8 0.8 0.8 0.8 0.8 0.8
1) BA/MMA graft copolymer
2) HCH-508 (trade(brand)name)
3) three-(2-hydroxyethyl) isocyanuric acid esters
4) TriMethylolPropane(TMP)
Table 3 has shown the yellow value (b-value) at the weathering time test.
Example 2 yellow values
The moon several 048 12 16 20 24 28 32
B-value Y6 3.3 4.1 4.5 6.4 6.6 7.2 7.7 5.9 6.3
B-value Y7 2.8 4.1 5.4 6.2 7.1 8.0 6.5 5.7 5.5
B-value Y8 3.0 3.8 4.0 5.1 6.8 7.6 7.0 5.4 5.9
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 bubble amts, type and HCl value
Y6 Y7 Y8 X5 Y9 Y10
Bubble amt 19 68 33 19 23
Foam-type is slight little slight greatly
HCl value 37 35 35 34 34 34
When calcium/aluminium/carboxylate salt hydroxy and calcium/aluminium/hydroxy phosphite common combination, Y6-Y8 has embodied optimum synergy in the example.Obtain improvement with X1 or the more initial color of X5.After weathering exposed, X6-X8 was very low in the lift velocity of yellow value in the comparative example Y1-Y4 example.And, be applied in the TMP among example Y9 and the Y10, with routine X5 and X3 relatively, be polyvalent alcohol further.Here be apparent that itself and Ca especially
4Al
2(OH)
12HPO
3. (fumaric acid esters) 3H
2O or Ca
4Al
2(OH)
12HPO
3.3H
2O and hydrotalcite combination embody extraordinary weather resistance characteristic and reduce and bubble.
Following mask body formulation examples 3-example 4, component (I), (II), (III) composite thermal stabilizer based on the structure invention, difference according to purposes, adding other functional agents and LDPE (melting index 0.2-10) is mixed, through known granulation process, be processed into multi-functional composite assistant master batch material:
Example 3 is applied to the stablizer higher derivative formula of master batch of the outdoor PVC section bar of white
LDPE(BASF?1810E) 30-70
Impact modifying agent BA/MMA graft copolymer 0-45
Ca
4Al
2(OH)
12HPO
3.3H
2O 1-30
Ca
4Al
2(OH)
12HPO
3. (fumaric acid esters) 3H
2O 1-30
The cured 0.5-5 of acid amides
2-hydroxyl-4-anisole ketone 0.5-5
Glycerine two hard ester acid phthalate 0.5-10
Dihydroxyphenyl propane 0.5-5
Phenmethyl stearyl methane 0.5-5
Acetylacetonate calcium 0.5-5
Hydrotalcite (Haichuan Company HCH-508) 1-20
Three-(2-hydroxyethyl) isocyanuric acid ester 0.5-5
Zinic stearas 0.5-10
Example 4 is applied to the thermo-stabilizer higher derivative formula of master batch of PVC translucent package film
LDPE(BASF?6001L) 30-70
Ca
4Al
2(OH)
12HPO
3.3H
2O 1-30
Ployethylene Wax 0.5-5
2-hydroxyl-4-anisole ketone 0.5-6
Glycerine two hard ester acid phthalate 0.5-10
Dihydroxyphenyl propane 0.5-5
Phenmethyl stearyl methane 0.5-5
Acetylacetonate calcium 0.5-5
TriMethylolPropane(TMP) 0.5-5
Zinic stearas 0.5-10
Epoxy soybean oil 5-50
Processing aid 2-10
Hydrotalcite (Shenzhen Haichuan Company HCH-508) 0.5-10
Claims (13)
1, a kind of polyvinyl-chloride use composite thermal stabilizer, be the composition of following (A), (B), (C) three kinds of structural constituents: composite thermal stabilizer is 100 weight parts.
(A), the hydrotalcite crossed of the nature of 1～80 weight part or processing treatment;
(B), at least a calcium-aluminium-compound hydroxy of 0～70 weight part, this compound can be selected from: (1) is 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 or the like combinations, when 2≤x≤8, y ≠ 1;
(C), at least one polyvalent alcohol of 0～70 weight part 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-, selectable have: propanedioic acid, Succinic Acid, lipid acid, fumaric, maleic acid, phthalic acid, m-phthalic acid, terephthalic acid, pyridine acid, M-nitro benzoic acid, salcylic acid, tartronic acid, oxysuccinic acid, tartaric, Bing Tongersuosuan, oxosuccinic 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, resemble propylene glycol, tris(2-hydroxy ethyl)isocyanurate, glycerol, propyleneglycoles, neopentyl glycol, kapok alcohol, Xylitol, arabitol, melampyrum, iditol, N.F,USP MANNITOL, Sorbitol Powder, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol and tripentaerythritol all can be used.
4, composite thermal stabilizer according to claim 1 is characterized in that, it is added in the polyvinyl chloride, and weight ratio is 0.2-6.5% (the thermoplastic resin weight 100% with halogen is calculated).
5, the senior derivative composition of the described one package stabilizer of a kind of claim 1, its recipe ingredient is:
Composite thermal stabilizer 1～50%;
LDPE (melting index 0.2-10) 30～70%;
Other multiple functional aids 1～50%,
Above-mentioned each component sum is 100%,
All per-cent is the weight percent of the higher derivative auxiliary agent master batch material of composite thermal stabilizer.
6, the senior derivative composition of composite thermal stabilizer according to claim 5, it is characterized in that described other various functional aids have: organic tin salt, softening agent, antioxidant, UV light absorber, static inhibitor, fire retardant, impact modifier.
7, the senior derivative composition of composite thermal stabilizer according to claim 6 is characterized in that, described organic tin salt can be methyl-, butyl-or tin octylate carboxylate salt, the MALEIC ANHYDRIDE of half esterization or thiol group salt.
8, the senior derivative composition of composite thermal stabilizer according to claim 6, it is characterized in that, described softening agent can be from following selection: the O-phthalic acids, resemble dimethyl phthalate, diethyl phthalate, dipropyl phthalate, butyl octyl phthalate, dicyclohexyl phthalate etc.; Softening agent with auxiliary stabilization, organic phosphorous acid ester, tricresyl phosphite aromatic ester for example, as triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, three (2,4-two-tert-butyl-phenyl) phosphorous acid ester; Phosphorous acid alkane aromatic ester and for example is as phosphorous acid biphenyl one monooctyl ester, phenyl dioctyl phosphite; Blended phosphorous acid alkyl nonyl phenylester, tricresyl phosphite alkane ester is as phosphorous acid tridecane ester, trioleyl phosphate, tricresyl phosphite stearate; Based on tetramethylolmethane, dipropylene glycol and dihydroxyphenyl propane, as the few candy ester of phosphorous acid.
9, the senior derivative composition of composite thermal stabilizer according to claim 6 is characterized in that, the agent of described antioxygen flower can be a phenol antioxidant, as 2,6-two-tertiary butyl-4-phenol, styrenated phenol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 2,2 '-two-(4-resorcinol) propane, octadecyl-3-(3 ', 5 '-di-t-butyl-4-resorcinol) acrylate, tetramethylolmethane-four-[3 ', 5 '-di-t-butyl-4-resorcinol] acrylate].
10, the senior derivative composition of composite thermal stabilizer according to claim 6 is characterized in that, described static inhibitor can be polyoxyethylene glycol, monostearate glycerine, hydroxy sulfonate.
11, the senior derivative composition of composite thermal stabilizer according to claim 6, it is characterized in that, described lubricant can be calcium stearate, Zinic stearas, fatty acid ester and aminocompound, O-phthalic acid glycerol two hard ester acid esters, Stearyl alcohol, 18 lipid acid, paraffin, Ployethylene Wax, acid amides is cured.
12, the senior derivative composition of composite thermal stabilizer according to claim 6 is characterized in that, described fire retardant can be ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide, aluminium hydroxide, zinc.
13, the senior derivative composition of composite thermal stabilizer according to claim 6 is characterized in that, described anti-properties-correcting agent can be the chlorination polyethylene, as Butadiene co-polymer, the rare terpolymer of Butadiene/third.
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|---|---|---|---|
| CNB031099564A CN1333009C (en) | 2003-04-10 | 2003-04-10 | Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition |
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|---|---|---|---|
| CNB031099564A CN1333009C (en) | 2003-04-10 | 2003-04-10 | Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition |
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| CN100386371C (en) * | 2006-03-28 | 2008-05-07 | 广东工业大学 | Polyol composites and use thereof in calcium zinc composite heat stabilizer |
| CN101671447B (en) * | 2008-09-11 | 2011-11-23 | 杭州三叶新材料股份有限公司 | Liquid heat stabilizer special for cable wires |
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| CN105385072A (en) * | 2015-12-23 | 2016-03-09 | 广东信诚达科技有限公司 | PVC calcium/zinc heat stabilizer and auxiliary heat stabilizer thereof |
| CN105504575A (en) * | 2015-12-03 | 2016-04-20 | 广东炜林纳新材料科技股份有限公司 | Composite heat stabilizer for PVC (polyvinyl chloride) |
| CN105579523A (en) * | 2013-09-27 | 2016-05-11 | 积水化学工业株式会社 | Molding resin composition including chlorinated vinyl chloride-based resin, and molded article thereof |
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| AU7765394A (en) * | 1993-12-03 | 1995-06-08 | Geon Company, The | Lead-free conductor coverings |
| AU1169395A (en) * | 1994-02-18 | 1995-08-31 | Sumitomo Chemical Company, Limited | Poly (vinyl chloride) resin composition and process for producing the same |
| DK1327662T3 (en) * | 1995-10-13 | 2005-07-25 | Crompton Vinyl Additives Gmbh | Stabilizer combinations for chlorine-containing polymers |
| ATE240365T1 (en) * | 1998-01-16 | 2003-05-15 | Crompton Vinyl Additives Gmbh | STABILIZER SYSTEM FOR CHLORINE-CONTAINING POLYMERS |
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| CN101671447B (en) * | 2008-09-11 | 2011-11-23 | 杭州三叶新材料股份有限公司 | Liquid heat stabilizer special for cable wires |
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| CN105579523B (en) * | 2013-09-27 | 2018-06-08 | 积水化学工业株式会社 | Forming resin combination and its formed body containing chlorinated vinyl chloride-based resin |
| CN105579523A (en) * | 2013-09-27 | 2016-05-11 | 积水化学工业株式会社 | Molding resin composition including chlorinated vinyl chloride-based resin, and molded article thereof |
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| CN105385072B (en) * | 2015-12-23 | 2018-02-23 | 广东信诚达科技有限公司 | PVC calcium zinc heat stabilizers and its auxiliary heat stabilizer |
| CN105385072A (en) * | 2015-12-23 | 2016-03-09 | 广东信诚达科技有限公司 | PVC calcium/zinc heat stabilizer and auxiliary heat stabilizer thereof |
| CN106009379A (en) * | 2016-06-21 | 2016-10-12 | 肇庆市森德利化工实业有限公司 | Magnesium-aluminum-zinc environment-friendly stabilizer special for U-PVC calendered sheet |
| CN106317911A (en) * | 2016-08-19 | 2017-01-11 | 深圳市志海实业股份有限公司 | Compound stabilizer based on polybenzimidazole and preparation method of compound stabilizer based on polybenzimidazole |
| CN108003390A (en) * | 2017-12-05 | 2018-05-08 | 广州市联诺化工科技有限公司 | A kind of compound organo-tin het stabilizer of environment-friendly type and preparation method thereof |
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| CN107955295B (en) * | 2017-12-08 | 2020-05-19 | 广东工业大学 | Auxiliary heat stabilizer and preparation method and application thereof |
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Assignee: Shenzhen Oceanpower Chemical Technology Co., Ltd. Assignor: Haichuan Industry Co., Ltd., Shenzhen Contract fulfillment period: 2008.8.9 to 2015.1.17 contract change Contract record no.: 2008440000274 Denomination of invention: Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition Granted publication date: 20070822 License type: Exclusive license Record date: 20081014 |
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