TWI241317B - Aluminosilicate stabilized halogenated polymers - Google Patents

Abstract

The present invention describes halogenated polymer resins stabilized with one or more co-stabilizers, at least one co-stabilizer comprising a synthetic crystalline aluminosilicate of the formula M2/nO.Al2O3.ySiO2.wH2O, in which M is a charge balancing cation, n is the valence of M and is 1 or 2, y is the number of moles of SiO2 per mole of Al2O3, and is 1.85 to 15 with a preferred range of about 2 to 5, and w is the moles of water of hydration per molecule of said aluminosilicate, wherein said aluminosilicate has a mean crystallite size in the range of about 0.01 mum to about 1 mum and a mean particle size in the range of about 0.1 to 10 mum. Also described is a method for stabilizing halogenated polymers such as PVC and CPVC by incorporating said aluminosilicate into a formulation thereof. A zeolite process improvement for creating a dehydrated zeolite that does not substantially rehydrate is also described. The zeolite created by such process is ideal for use as a co-stabilizer of halogenated polymer resins.

Description

1241317

Cross-Reference to Related Patent Applications The present invention claims the priority of US Patent Application No. 09 / 363,337 filed on July 29, 1999 and filed on July 29, 1999. Η Λ,,%, and Continued Applications in the Ma Child Case . BACKGROUND OF THE INVENTION The present invention relates to a chemical polymer and a modified method for stabilizing it. More specifically, the present invention relates to The heat of chemical polymer resins that are processed into shaped objects. The chemical action is particularly rampant. The present invention relates to the use of a synthetic crystal bauxite salt, or for this purpose ... The thermal stabilization effect of this resin. Self-containing polymers, such as poly (vinyl chloride), chlorinated poly (ethylene chloride) (CPVC), and other chlorine-, gas-, or bromine-containing polymers made at temperatures higher than 15 (rc) unless added Stable, otherwise it is easy to degrade and fade even if it is only maintained for the short period of time required for continuous processing at these temperatures. When this happens, the polymer will either be unusable or cause a very high yield. The rate of return of goods and the ability to recover and reuse waste from the process will also be severely impaired. Subsequent processing of this resin and the products made from this polymer will not be stable unless properly dyed Otherwise, the quality is also easy to deteriorate. As the time under the sun or purple material is prolonged, it will become broken and fragile or fragmented, and therefore useless for every original purpose. When the material is molded into a finished object At the same time, these resins are also easy to form thin sheets on processing equipment, such as casting molds, ball mills or calender rolls, in their unstabilized form. This is due to the defect -4 in objects made from this resin. -This paper Applicable to China National Standard (CNS) a4 specifications (21〇 &lt; 297 mm) 1241317 V. Description of the invention (steel, and tends to require frequent cleaning equipment, but also leads to lack of production work =; material: Under the degree of processing, the processing of unstabilized PVC: 1: In terms of high temperature. ^ ^ 'Processing will quickly lead to degradation, and the system will fade, hydrogen chloride will be emitted, and the surface will be flat. Adhesion to processing equipment = All the mechanisms of these instabilities are still uncertain and may be Nanhua polymers; especially beta production ..., beer qing /, _pvr.,, Lailai ethylene (PVC) or gasification polymer The other symbolic forms of ethene, dioxin have already been shown in hydrogen chloride. The fact that lice reduction will further promote catalytic degradation is well known. To prevent such degradation, hydrogen chloride must be kept at a very low concentration. , And / or neutralize it during processing. Traditional methods for stabilizing polymers such as PVC have focused on the application of various <inorganic, organometallic, and organic stabilizers. Adopted Stabilizers include, for example, dibasic, tribasic, and tetrabasic lead sulfates; dibasic lead phosphite; and white lead. Commonly used (organometallic stabilizers include, for example, barium, cadmium, tin, tin, magnesium Organic derivatives of heavy metals such as zinc, zinc, and / or zinc often form mixtures with other co-stabilizers and other traditional additives. Organic stabilizers that have been used include, for example, calcium fertilizer packages, various esters of various fatty acids Compounds, phosphites, thioesters, β-diketones, etc., either alone or in combination with organometallic stabilizers such as foot stabilizers for these resins. Oncite salts or zeolite molecular sieves have also been used. Proposed as a stabilizer for PVC 'For example, US Patent No. 3; 245,946 discloses the use of activated zeolite a as a stabilizer for PVC, and US Patent No. 4,000,100-5- 1241317 A7 B7 V. Description of the invention (combined application of unactivated, fusi 3A, 4A, or 5 molecular sieve, and a traditional organometallic or organic stabilizer mixture.纟 It is known to use a complex primary and secondary stabilizer system, including as a stabilization system-a type of curse J-type, crystalline, synthetic hydrous aluminosilicate with a range of 13 to 25% crystal water The water content, such as No. *, does not, as disclosed in the US patent case. In previous techniques in which stone or salt was used as part of the stabilization system of PVC resins, 'the focus was focused on factors such as the crystal water content, and / or the pore size of the onyxate, The preferred μ stone particle size range is also documented, assuming that certain size ranges will give the best dispersion, and enhanced physical properties, such as tensile strength and modulus, such as other solid polymers such as calcium carbonate Known additives. However, we did not perceive the direct relationship between the invention of the prior art to establish or propose the reduction of particle size and the improvement of thermal stability, nor did we perceive the relationship between the invention of the prior art and the particle size and crystal size of the invention. The area's other distinct connections. The traditional stagnant stone system consists of small cubic or orthorhombic crystals and / or other geometric forms, such as rhombus, twelve-sided_open <: small spheres, octahedrons, etc. 'and their combinations and their interactions: composition, Έ: we will Condensed into particles. The degree of agglomeration and the six-and-human interaction &lt; determines the distribution of particle size. This distribution of blood punishment &amp; + # '' the soil system uses a light scattering or other spectroscopic techniques to determine: however the crystal size is actually Insects are not relevant, and are typically measured using scanning electron microscopy imaging technology. As an example of this difference, currently available in the market%> Fu Shi 4A and faujasite 1 Fu Shi 1 female, with -This paper size from 1.0 to 5.0 microns applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6, 1241317

It is especially small, with an average particle size of about 30 to 100 or more micrometers, although the prior art has discovered that the particle size reduction method is not discussed in terms of preparation as in this patent application Procedure for preparing small crystal zeolite for patent application in the case. The application of factors such as the stabilization system and the activation of zeolites has led to a substantial improvement in the ability of aluminosilicates to stabilize PVC resins, but further improvements are needed, especially in In terms of the degree of thermal stabilization of PVC, CPVC and other polymers. Accordingly, the main object of the present invention is to provide an improvement in the thermal stability of polymer molding resins such as PVC, CPVC, and other halogenated polymers used to make articles at elevated temperatures. SUMMARY OF THE INVENTION It has been found that according to the present invention, by using aluminosilicate as a stabilizing component of this halogenated polymer, some or other improvements in the stability of the polymerized resin are obtained. The individual crystals of the aluminosilicate have a fine crystal size ranging from about 0.01 micrometers to about 10 micrometers. Surprisingly, it has been found that although the particle size is important to maintain the physical properties of the polymer system, the use of aluminosilicates with fine crystal sizes is responsible for the thermal stabilization of these polymers. Further improvement of the role is critical. Such fine crystal particle size stabilizers are usually used in combination with conventional inorganic, organometallic, or organic co-stabilizers. In addition, it has also been found that, for example, in CPVC and hard PVC formulations where T requires a higher aluminosilicate concentration relative to soft PVC coatings, 1241317 A7 B7 V. Description of the invention (a range from about 0.5 to about The particle size in the range of 3 microns is better; moreover, maintaining a very low degree of aluminosilicate hydration is important to prevent the generation of blisters. The steam of the silicate is dehydrated to The dehydration effect of water content less than 8% by weight of aluminosilicate prevents the rehydration of gallate to a water content of more than 10%. When used in formulations containing extremely high zeolite concentrations, this steam is The burnt dehydrated stagnant stone is particularly suitable for preventing or minimizing blisters. DESCRIPTION OF THE INVENTION Generally, the present invention includes a molybdenum decree, ^ 〇,.% Working polymer, which contains -A commercial polymer resin and ―synthetic crystal salt of an amount sufficient for stabilization, the crystal salt has a fine average crystal size in the range of about 0.01 micrometer to about 1.0 micrometer, and is better Yes-in the range of about 0.2 to about i microns And preferably an average crystal size in the range of about 02 to about 0.85 microns. Although the crystal size is important to the present invention, the particle size can generally be varied over a wide range, but it is better It is used with an average particle size in the range of about 0.1 to about 3 microns, and more preferably, for CPVC and rigid PVC formulations, and more preferably, for CPVC and rigid PVC formulations. Within the present invention is a method for stabilizing such compounds by mixing a polymer with the foregoing phosphonates alone or in combination with a host, organometallic, and / or organic co-elixir. == Yu: Invented polymer resins "chemical polymer resins, including but not limited to 1 (N 1 ethyl acetate (PVC) 'gasified poly (ethylene chloride) (CPVC), polytrimethylene-neodymium (Ne0prene)'-a kind of propionate Nitrile_gas acetic copolymer ⑴㈣ 、 一

1241317 A7 B7 V. Description of the invention (6) Polyethylene acetamidine-acetic acid acetate copolymer, polyvinylidene chloride, a polytetrafluoroacetamidine-air acetamidine copolymer, or a polyfluorovinyl chloride The polymer is preferably a self-chemical ethylene polymer resin. Polyethylene and gasified polyvinyl chloride are particularly preferred resins used in the present invention. The present invention can be applied to both hard and flexible PVC formulations. As used herein, a "hard" formulation is defined as having a plasticizer or a combination of plasticizers, and / or a concentration of zero. To less than about 5 parts of elastomer per hundred parts of resin (phr); a "soft" formulation typically has a plasticizer from greater than about 5 up to about 50 ph. CPVC formulations typically only have hard formulations. The PVC used in the present invention can be one of several types, and its properties will change. Depending on the polymerization method and the temperature of the polymerization reaction, the higher the temperature of the polymerization reaction, the lower the molecular weight of the PVC produced. . A typical PVC resin has an average molecular weight 'in the range of about 20,000 to about 100,000, and a Fikentscher K 値 ranging from about 41 to about 98. For specific applications, certain molecular weight PVC resins exhibit the best physical properties and process capabilities. In general, suspended PVC resins are more thermally stable than PVC resins made using agglomerates or emulsion polymerization. Depending on the polymerization method and manufacturing conditions, p V C can change its resin particle size and porosity, and the same formulation can have different performances. The aluminosilicate used in the present invention is a synthetic crystalline aluminosilicate, commonly referred to as "zeolite". Zeolite is a material with independent pipes and voids that allow small particles to diffuse into and out of its crystal structure. The function of these materials That is, it is a microstructure that allows access to a large number of internal surface areas and increases the capacity for adsorption and ion exchange. -9-Applicable to Chinese Standard (CNS) △ Dimension X297mm) '' &quot;-

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The aluminosilicate or a M2 / nO.Al203.ySi〇2.wH2O useful in the present invention is designated by and / a, and σ is represented by the chemical formula, I, /, where M is the positive ion of the charge balance. The number of horses and horses 1 may be about u to about 15, and the number of moles per eight children = two cuts 2) and the number of hydrated water moles of the W salt substituted by ^ in the chemical formula is appropriate. Charge balance cations such as sodium, potassium, zinc, and magnesium include silver, cadmium, sodium, potassium, alkyl and / or aryl ammonium, lithium, ammonium, ions, ',',:, strontium, nickel, iron, And their mixtures, such as cations, (the cations are alkali metal and / or alkaline earth metal cations, and if the mixture contains sodium and / or tritium metal or earth metal, M'd is preferably potassium and / or The calcium content is less than about 35% by weight of the total alkali metal or alkaline earth metal content. • The silicon dioxide per molecule of the aluminosilicate represented by 7 in the chemical formula, 2) the number of ears, may It is in the range of about 18 or higher, but it is still suitable for horses, 1.85 to about 15, more preferably about 1.85 to about 10, and preferably between about 2 U 5 || For certain specific embodiments described below, * is in the range of about 1.8 to about 3.5. The mole number of water in the zeolite represented by w as the hydration water in the formula is suitable β is greater than about 0.1, more preferably in the range of about ο. 1 to about 10. The zeolite framework is composed of Si04 tetrahedron connected by a common oxygen atom. Instead of silicon, a charge imbalance is generated. A non-frame cation is needed to balance the charge. These cations are contained in the pipes and voids of these materials. 'Can be replaced by other cations that impart ion exchange properties. Although the frame can undergo some distortion, the water in these materials can be removed reversibly and the main structure remains intact. In addition, these -10-this paper size applies the Chinese national standard T5 ^ i ^ (210X297 · — 1241317 A7 B7 V. Description of the invention (X ------:-V 8 'type is alkaline, low Silicon dioxide / oxidation ratio (Si〇2 / Al203) ratio: The suspension in this water will usually give-値 greater than 9. The combination of porous structures of these compounds with high alkalinity is believed to be responsible for these Weishi, by neutralizing the acids released during processing and producing inert salts and / or plundering excess cationic metals, is responsible for most of the ability to stabilize the self-polymerizing polymer. Stagnation is usually based on its crystal units Plenum structure to classify (see WMMeier, DHOlyn, and Ch. Baerlocher, Elsevier Press, 1996 "Illustration Collection of Zeolite Structure Types" Fourth Edition), those suitable for use in the present invention for stability Agents include compounds with characteristics such as zeolite A, zeolite p, zeolite X, and zeolite γ. Although other zeolites can also be used in the present invention, the preferred aluminosilicate is still zeolite A. Che Yihao疋 'use a completely anhydrous Buddha stone, that is, a kind of Many of the hydrated hydrate salts have been removed by dehydration before being added to the formulation of the polymer. This product is often known by the artist as M-activated zeolite. Suitable activated zeolites that are particularly useful in the invention are those that have been dehydrated to a water content between about 0. to about 20% by weight of the aluminosilicate, and advantageously between about 0.5% to about 18%, and most suitably between about 1% and about 15%. In a preferred embodiment described below, the zeolite is burned by steam to a temperature below about Water content of 8% by weight of zeolite. What I also want is that the aluminosilicate has an average particle size in the range of about 0.1 to about 10 microns, and desirably at least about 90% of the particles are less than about 50 Micron, advantageously less than about 25 microns, and most suitably less than -11-this paper size is suitable for financial ® S Family Standard (CNS) A4 specifications _ x 297 public love) 1241317 A7 B7 five invention description (about 10 microns; What I also want is that the aluminosilicate has an almost uniform pore in the range of about 2.8 to about 8 Angstroms (A) Diameter, and / or an external surface area in the range of from about 3 to about 300 square meters per gram. As indicated previously, the above identified silicates can be used with polymers and with traditionally used PVC resins. The stabilizing co-stabilizers are suitably formulated. Suitable stabilizers include organometallic complexes such as magnesium, antimony, cadmium, barium, tin, zinc, and / or lead, such as various fatty acids. Organic complexes of polyesters, β-diketones, organic phosphites, blocking amines, organic thiols, epoxidized oils, epoxy compounds, and / or phenolic feet, such as Inorganic faults such as dibasic, tribasic and / or tetrabasic lead sulfate, dibasic lead phosphite, and / or white lead: substances, and / or such organometallic, organic, and inorganic Various combinations of sexual complexes. The present invention provides a method for stabilizing a polymer resin according to the method of the present invention, which comprises combining the resin with a synthetic crystalline aluminosilicic acid containing a chemical formula of M2 / n〇Al2〇3.ySi〇2.wH2〇 Salt stabilizer 2 where M, Π, y * w are as defined above, wherein the aluminosilicate has an average crystal size in the range of about 0.01 micrometers to about 1 micrometer. In carrying out the process viewpoint of the present invention, the aluminosilicate can be mixed with the polymer during the polymerization process, during or after the aluminosilicate, and mixed with the polymer during the manufacturing process. . From the viewpoint of the composition of the present invention, it is also preferable that the acid salt has an average particle in the range of from about to about 10,000 m: It is preferable. The amount of added zeolite and zeolite depends on the coating effect and the type of resin used. '12 -1241317 A7 B7 V. Description of the invention (1) The compound is sufficient 'For example, most of them have extremely large amounts. In soft PVC formulations with plasticizers, the effective amount of zeolite can typically be in the range of about phr or lower, but larger amounts can be used if necessary; in the presence of little or no plasticizer In hard PVC and CPVC formulations, the effective amount of zeolite typically ranges from about 0_05 to about 10 phr. As noted above, when the amount of zeolite is increased, the zeolite particle size becomes more important due to its potential impact on the physical properties of the plastic. For example, the larger particle size stagnation stone has a negative impact on impact resistance and tensile and flexural strength. Therefore, what I want is for hard PVC and CPVC coating. Smaller particles of zeolite. Because we want to reduce the particle size without damaging the zeolite crystal structure, the lower limit of acceptable particle size is limited by the crystal size. Therefore, when the smaller particle size zeolite is what σ wants, it is also used. Zeolites with extremely small crystal sizes are preferred. The extent of hydration, the nature of exchangeable cations, the choice of co-stability, and the pore diameter are known to be important considerations in the ability of aluminosilicates to impart thermal stability to halogenated polymers. However, it has been roughly found that the further improvement of the aluminosilicate's ability to confer further thermal stability is that the body size is the most critical factor. However, as noted above, particle size also becomes critical in coatings that use zeolites with increasing south concentration; in particular, the degree of hydration in such coatings becomes even more critical. . In the extrusion molding operation, zeolites with a concentration greater than about 1.2 were found to release blisters in the extrusion molding solution. (CNS) A4 specification (210X297) -13-1241317, which can dehydrate zeolite by the method of hydration,

Degree, "We have found that it is better to scorch, and the steam under i conditions will not be lost at all. This dehydration is well-known in the dehydration ..., the degree of privacy is also known to be sufficient in the art. Structure, temperature, steam content, and pressure; In addition, on the other hand, the scorching effect will destroy the steam burning conditions of the crystals of the stone, but it still maintains the crystallinity of the pebble, but also leaves behind. We have found that accepting low-silica-to-aluminum zeolites with suitable yields will result in "minimum damage to the crystal structure. Fu Shi / ,, &quot; Coin stone, is ideal for co-stabilizing polymers. Once a Monday &gt;# τ ^ ^ ^ Luo / Ια is 100% steamed, steamed, and gaseous at a rate of about 20% to about 1000% for a period of time and maintains a pressure sufficient to dehydrate the sludge to one: It contains 8% or less of water content, and on the other hand, it maintains at least about 400 to about 700 degrees. The scorch temperature of 0 has been found to prevent rehydration of dehydrated stagnation to a water content above about 10% by weight of stagnation. For example, it has been effective to use the steam at 50% of 65 (rc steam at atmospheric pressure for hours, but also try to burn for 1 to 5 hours with 100% of steam at 400 Torr; or vice versa 20% to 80% of 70 ° C steam can be effective for 15 minutes to 丨 hours. Surprisingly, only the larger particle size material is ground to a finer particle size alone, without It will make a significant contribution to the improvement of thermal stability, but rather the size of the crystal itself, as opposed to the agglomerated particles of the crystal, in order to obtain stability these improvements must be reduced to the above range. Although the stability to -14-this paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1241317

Generally, the lower soft PVC inch is very comfortable. The stone crystal ruler requires more important coatings than $ # €%. For example, as described above, the kimono ™ and cakiki are as above. By. Therefore, the size of the donor's body for both the "material" and the "growth" is very much ... in terms of stone concentration, 'particle size and crystal small society, and the larger particle size material is ground to a finer size related to sex. The particle size provides the improvement we want. &Amp; What we want is to perform the particle size shrinking step carefully to prevent the breakage of the fine crystals obtained according to the invention or to minimize. ， ° 曰 Said that during the production of Mingshi Xiate, the use of-the liquid containing the core to control the growth of crystals (solution A) to achieve crystal size reduction in Mingzhuang acid process, as shown in the following detailed preparation examples Show. Example 1 Synthesis of solution A and 4 pharmaceutical grade sodium hydroxide pellets (3 16.3 g) were added to deionized water (3 16.3 g) and stirred until the solution was clear, then the solution was heated until boiling, and slowly Aluminum trihydrate (63 · 1 g) was added to the stirred solution until it dissolved, then the solution was cooled to below 100 ° C and deionized water (1090.4 g) was added. Slowly add a 2.0% solution of sodium silicate (ι, 237.5 g, silica / sodium oxide = 2.0, 56% by weight of water) to the agitated aluminate and allow it to age before use. At least 12 hours. : Synthesis of fine crystalline 4A zeolite-Example 1B Adding reagent-grade sodium hydroxide pellets (203.5 g) to deionized water (203.5 g) -15- This paper size applies Chinese National Standard (CNS) Α4 size (210 X 297 Mm) 1241317 A7 ------------ B7 __ V. Description of the invention (") I 〇 and stir until the solution is clear, then heat this solution until stagnation 'and slowly Add aluminum trihydrate (i 62 0 g) to the stirred heated solution until it dissolves, then cool the solution to less than 10 (rc, dilute with deionized water (180 g), and further cool to 6 〇 ° C. Separately, a solution of deionized water (1,615 g) to a 2 · 0 ratio of sodium silicate (395 g of 'silicon dioxide / sodium oxide = 2.0, 56% by weight of water) solution Dilute and stir until homogeneous. Within 5 minutes, add the aluminate solution obtained from the previous paragraph to this solution by low-level stirring, and then stir the above solution A (3 8.7 g) into a solution. The mixture was placed in a water bath, heated to 94 ° C, and continuously stirred at this temperature for about The formed slurry was filtered and re-soaked into a slurry in room temperature deionized water (1.0 liter, the pH was adjusted to 10.5 with sodium hydroxide) and filtered. This washing procedure was repeated again and The powder was ordered to dry for about 12 hours at 100 ° C. Example 1B is summarized in Table 1 together with additional samples (Examples 1A and 1C) prepared using the same procedure, but replaced with the test doses shown in Table 1. Table 1. Small crystals 4 A; Synthetic composition of ephedrine 2.0> oxalate (g) Example 1A 382 Example 1B 354 Example 1C 271 Water-crushed acid salt (g) 1,565 1,550 1,550 50% by weight) (g) 400 388 352 ATH (g) 162 162 162 Solution A (g) 77.4 155 387 Water-ming salt (g) 220 225 200 Total weight (g) Average crystal size (microns) 2,806.4 0.6 2,834 0.4 2,922 0.3 The following examples 2A, 2B and 3 are based on Zeolite Molecular Sieves, D. Break, Krieger Publishing Company, -16, Chapter 4, pages 260-274. This paper size is in accordance with China National Standard (CNS) A4 (210X297) Mm) 1241317 A7 B7

V. Description of the invention (14

Malabar, Florida. The steps are as follows: Example 2A 4A boiling anti-primary gold prepared by a laboratory method. Add reagent-grade sodium hydroxide pellets (207 g) to deionized water (207 g) and stir until the solution is clear. Heat the solution until it boils, and slowly add aluminum trihydrate (162.0 g) to the stirred solution until it dissolves. Then let the solution cool to below 100 C. Add deionized water (240 g) and let It is cooled to 60 ° C. A deionized water (1,130 g) was used to dilute a 2.0 ratio solution of sodium silicate (408 g, silica / sodium oxide = 2.0, 56% by weight of water) and stir until homogeneous. Within 15 minutes, add this solution to the aluminate with low stirring, then place the mixture in a water bath, heat to 94 ° C, and continue stirring at this temperature for about an hour. The formed slurry was filtered and re-soaked into a slurry in room temperature deionized water (1.0 liter, pH 値 was adjusted to 10.5 with sodium hydroxide) and passed through a 遽. Repeat this washing procedure again and 100Ό ordered the powder to dry for about 12 hours. The zeolite crystals formed had an average crystal size of 3.0 microns and an average particle size of 6 · 53 microns.

Example 2B 4A zeolite will become known 4 pharmaceutical grade sodium hydroxide pellets (207 g) were added to deionized water (207 g) and disturbed until the solution was clear, and then the solution was heated until boiling 'and, Add aluminum trihydrate (162.0 g) to the stirred solution until -17-1241317

It is allowed to dissolve, and then the solution is cooled to less than 0 (rc, deionized water (240 g) is added, and allowed to cool to 60 ° C. Deionized water (1,130 g) is used to a 2. 〇 Proportion of sodium silicate (408 g, silicon dioxide / sodium oxide 2.0, 56% by weight of water) solution was diluted and stirred until homogeneous. Within 15 minutes, the Aluminate was added to this solution, then the mixture was placed in a water bath, heated to 94 ° C, and kept stirring at this temperature for about an hour. The resulting slurry was filtered and deionized water at room temperature Refoam into a slurry (1.0 litre 'adjust the pH to ι0.5 with sodium hydroxide) and filter, repeat this strip washing procedure again and let the powder dry for about 12 hours under a loot. Opened &gt; The resulting product has an average crystal size of 1.25 micrometers and an average particle size of 3 micrometers. Table 2 · 4 Α> Synthetic composition of fusistone Example 2A Example 2B Addition instruction 2.0 silicate (g) 408 408 Water-silicic acid Salt (g) 1,130 1 V- / U 1 130 Sodium hydroxide (50% by weight) (g) 414 _ A 5 XU 414 ATH (g), 162 * 16? Water-aluminate (g) 240 ″ 240 Total weight (g) Average crystal size (micron) 2,354 3.0 ------ 2,354 A _____L25 Example 3 Synthesis of small crystal 13 X zeolite A 50% by weight sodium hydroxide solution (141 g) was heated until stagnation, and aluminum trihydrate (81 g) was slowly added to the stirred solution until it was dissolved, and then Allow the solution to cool below 100 ° C, add deionized water (55 g), -18-1241317 A7 ______B7 V. Description of the invention (16) and let it cool to room temperature. Deionized water (901 g) A 3.2 ratio solution of sodium silicate (194 g, silica / sodium oxide = 3.2, 62% by weight of water) was diluted and stirred until homogeneous. Within 15 minutes, the aluminate was stirred with low intensity Add to this solution 'then add solution A (387.5 g) to the solution' and place the mixture in a water bath, heat to 94 ° C, and maintain at this temperature for about six hours. The formed slurry was filtered and re-soaked into sludge (2.0 cm) in deionized water at room temperature. The pH was adjusted to ι0.5 · 5 with sodium hydroxide, and the pH was adjusted again. This washing procedure was repeated again and the powder was dried at 100 ° C for about 12 hours. This is the following example 3D. Additional examples were prepared with a similar procedure to change the amount of solution A, 3A to 3C, and the crystal sizes are summarized in Table 3. Table 3 · Small crystals 13 Synthetic composition of X hesitite Example 3 A Example 3B Example 3 C Example 3D Average crystal Size (micron) 0.4 0.3 0.2 0.2 Example 4 4A zeolite samples with different crystal sizes were synthesized into plasticized PVC formulations as shown in Table 4 The formulations for each set of tests were prepared from a common main batch, and The indicated amounts of zeolite were added and the main batch was prepared as follows: A Henschel high strength laboratory mixer was preheated to about 77. (: Then pvc resin (1,200 g) and epoxidized soybean oil (ESO) were charged and the mixture was taught at a speed of 3,000 revolutions per minute (RPM) 'when the blend reached 700. c, slowly-19- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm)-1241317 A7 B7 V. Description of the invention (17 Adding dioctyl phthalate (DOP) plasticizer, At 75 ° C, add zinc stearate and oxidized polyethylene wax and cool the mixture at 80 ° C and reduce the stirring to about 1900 revolutions per minute (RPM) when the temperature is below 45 ° The mixer was emptied at C. Then zeolite was added to each formulation as follows: The main PVC batch (300 g) and zeolite (0.59 g) were added to a food processing mixer. The mixture is mixed for 15 minutes. The dynamic thermal stability (DTS) test (ASTM test method D2538-95) is used to perform the thermal stability test of the powdered PVC compound. In the following examples, dts is defined as the equilibrium torque has been established After reaching the 20% torque increase time, the DTS test uses a Haake torque current under the following conditions To perform: 190 ° C, 100 RPM, and 63 grams of samples. (Table 4 · Compounds and properties) Ingredients (phr *) 1 2 3 4 5 ** PVC resin (Oxy 23 (l ·, K = 68) ) 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 50 Aldrich 0.3 0.3 0.3 0.3 0.3 Epoxidized soybean oil D-81 (Henkel) 2 2 2 2 2 Oxidized polyethylene wax AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 Example 1C 0.3 Example IB 0.3 Example 2B 0.3 Example 2A 0.3 DTS (minutes) 19 19 14 8 3.6 Zeolite properties Average crystal size (microns) 0.3 0.4 1.25 3.0--20- This paper size applies to Chinese national standards ( CNS) A4 size (210X297 mm) 1241317 A7 B7 V. Description of the invention (18 Frozen multi-point nitrogen BET surface area (cm² / g) 18 8 3 ----- 1 Average particle size (micron) 2.94- --- 98 4.49 Too 3.07 6.53 Relative crystallinity (%) ~ parts per hundred resin "Control group without zeolite as observed from the data in Table 4, when the crystal size is reduced from 3 to 0 At the micron, the performance of 4A zeolite as a stabilizer is significant The improvement, the further reduction of the body size increases the external surface area, but it is not good as it-the performance of the stabilizer 'cannot be directly related to the particle size. Example 5 This example uses large and small crystals of 4 A · zeolite to demonstrate the relative impact of particle size reduction on its performance as a PVC stabilizer. A micronizer ™ jet mill was used at 120 pounds per square inch ( The 4 A zeolite described in Example 2 was milled at a pressure of psi) to reduce its particle size. The zeolite was then synthesized into a plasticized PVC formulation as in Example 4 and tested under the same conditions. The formulation of Example 5 and the test results are shown in Table 5 below.

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(Table 5. Preparations and properties) Ingredients &lt; Preparations (phr) 1 2 3 4 5 PVC resin (Oxy 230) 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 Zinc stearate (Aldrich) 0.3 0.3 —0.3 0.3 0.3 Epoxidized soybean oil (ESO) D-81 (Henkel) 2 2 2 2 2 Oxidized polyethylene wax AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 Advera ™ 40 1P * 0.3 AdveraTM401P (—. — &Amp; ) 0.3 Example IB 0.3 -21-The size of the thread paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1241317 A7 B7 V. Description of the invention (19 Example 1B (milled once) 0.3 Example 1B (milled once) 0.3 DTS (Minutes) 10.4 9.6 20.0 19.1 18.2 Average particle size of zeolite (micron) 2.91 2.34 4.78 2.30 1.75 Average crystal size of zeolite (micron) 1.2 1.2 0.4 0.4 0.4 * For comparison, Advera ™ 401P, a commercial 4A aluminum Silicate zeolite, Advera ™ is a registered trademark of PQ Corporation. As observed from the data in Table 5, particle size reduction is not improved for small or large crystals. 4A zeolite is used as a PVC stabilizer of Yes; however, it should be noted that this example deals with a soft PVC formulation in which very low zeolite concentrations have been used, as described below with respect to Example 12, and the reduced particle size improves CPVC and hard PVC with higher zeolite loads. Example 6 Example 6 demonstrates the effect of reducing the crystal size of faujasite structure zeolite 13X on its performance as a PVC stabilizer, as in Example 4, zeolite X is synthesized into a soft PVC formulation and tested. Metrastat ™ oven, according to DIN 53 8 1F and AFNOR T5 1-224, for 2 hours at 190 ° C for a static thermal stability test using a Haake ™ twin-screw extruder at 1 75 ° The formulation was extruded at a raw material temperature of C to make a 1 X 0.04 inch strip for testing. The early colors of Metrastat ™ in the following examples are defined as the observable color change time; and Metrastat ™ is stable Degree is defined as the time required to observe complete degradation when the color changes to dark brown or black. Table 6 shows the formulations and test results. (Table 6. Preparations and properties) -22- This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1241317 A7 B7 V. Description of the invention (Ingredients, preparations (phr) 1 2 3 4 5 6 PVC resin (Oxy 230) 100 100 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 50 50 Aldrich 0.3 0.3 0.3 0.3 0.3 0.3 Epoxidized soybean oil (ESO) D-81 (Henkel &gt; 2 2 2 2 2 2 Oxidized polyethylene wax AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 0.2 Example IB 0.3 Example Advera ™ 201 * 0.3 Example 3A 0.3 Example 3B 0.3 Example 3C 0.3 Example 3D 0.3 DTS (minutes) 182 6.6 9.2 11 10.6 1 1.2 Metrastat ™ early color retention (minutes) 73 60.5 65.8 66.8 69.8-Metrastat ™ stability (minutes) 95.3 61.8 67 71.5 78 Average particle size of zeolite (micron) 4.7 5.64 12.2 10.5 15.8 8.4 Average crystal size of zeolite (micron) 0.4 3.0 0.4 0.3 0.2 0.2

For comparison purposes, Advera ™ 201, a commercial 13X onyxate zeolite, is a registered trademark of PQ Corporation. The analysis of the results in Table 6 proves that the reduction in the crystal size of X hematite improves its performance as a PVC stabilizer; however, a direct relationship with particle size cannot be observed; however, 'it should also be noted here that' At higher sludge loadings, particle size may be a factor. Example 7 Example 7 shows the performance of small crystal zeolites VIII and πχ under higher stabilizer load. The plasticized PVC compounds were prepared and tested under the conditions shown in Example 4, which are listed in Table 7, which is listed below. Shows the preparation and its preparation. -23- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) '--- 1241317 A7 ___ B7 V. Description of the invention (w). (Table 7 · Compounds and properties) • Ingredients (phr) 1 2 3 4 5 6 PVC resin (〇xy 230) 100 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 50 Zinc stearate ( Aldrich) 0.3 0.3 0.3 0.3 0.3 0.3 Epoxidized soybean oil (ESO) D «81 (Henkel) 2 2 2 2 2 2 Oxidation? Yes ethylene wax AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 0.2 Example IB 0.3 045 Example 3B 0.3 0.45 Example 3C 0.3 0.45 DTS (minutes) 16.4 25 11.9 16.4 11.3 14.7 As shown in Table 7, increasing the content of zeolites A and X improved the DTS of the PVC formulation; however, stagnation A was the best. Example 8 Example 8 compares the performance of other fossils as PVC stabilizers. A PVC formulation was prepared and tested as described in Example 4, and its evaluation is described in Table 8 below. (Table 8. Formulations and properties) Who is the component product? (Phr) 1 2 3 4 5 6 PVC resin (〇xy 230) 100 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 50 Alzrich 0.3 0.3 0.3 0.3 0.3 0.3% Oxidized Soybean Oil (ESO) D-81 (Henkel) 2 2 2 2 2 2 Oxidized Polyethylene Wax AC629A (Allied Sienal) 0.2 0.2 0.2 0.2 0.2 0.2 Example 1B ” 0.3 0.45 * Zeolyst CP 500C-11 Mercerizing; Fu Shi (Sodium Aluminosilicate) 0.3 0.5 -24- This paper size is applicable to Chinese National Standards &amp; NS) A4 specifications (210X 297 mm) 1241317 A7 B7 V. Description of the invention ( twenty two )

Sodalite 0.3 MAP Low SiO, / Al 2 03 P Zeolite 0.3 DTS (minutes) 13.3 22.5 4.6 4.7 6.7 5.6 * ZeolystTMS Zeolyst International Registered Trademarks The results in Table 8 prove that not all zeolites can be used as PVC stabilizers. The same performance, zeolite A is the better zeolite. 1 Example 9 Example 9 demonstrates the effect of heat-activated zeolite 4 A, which has a crystal size of 1.5 and 0.4 micrometers' was heated at the temperature shown below for four hours, using an ignition loss (LOI at 1000 C) ) To test the moisture content in the sample of stagnant stone a, prepare and test the PVC formulations as described in Example 4, and Table 9 lists the PVC formulations and their properties. (Table 9. Preparations and properties) Ingredients (phr) 1 2 3 4 5 6 7 8 9 10 PVC resin (Oxy230) 100. 100 100 100 100 100 100 100 100 10 DOP (Akcros) 50 50 50 50 50 50 50 50 50 50 Zinc stearate (Aldrich) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Epoxidized soybean oil (ESO) D-81 (Henkel) 2 2 2 2 2 2 2 2 2 2 2 Oxidized polyethylene wax AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Advera ™ 40IP * 0.3 Advera ™ 401P- 100 ° C 0.3 Advera ™ 401P-200 ° C 0.3 Advera ™ 401P-300〇C 0.3 Advera ™ 40IP-500 ° C 0.3 Example IB 0.3 Example IB-100 ° C 0.3 Example 1B-200 ° C 0.3 Example 1B- 300 ° C 0.3 -25- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 1241317 A7 B7 5 Description of the invention (23 Example 1B- 500 ° C --- 0.3 DTS (minutes) 8.4 10.6 12.4 12.3 13.0 20.5 21.0 22.3 21.7 16.7 Zeolite LOI (% by weight) 21.0 15.1 5.4 4.2 1.8 21.5 15.1 5.0 4.0 1.9 * For comparison With Advera ™ 40 1P, a refined 4 oxalate zeolite, Advera ™ is a registered trademark of PQ Company. The results in Table 9 prove that the degree of hydration of 4A zeolite affects its performance as a pVC stabilizer, the best range Range from about 4% to 22%; however, it should be noted that this example is about a soft PVC formulation with extremely low zeolite load. Example 10 Example 10 demonstrates the properties of Example 1B, a portion of which is exchangeable for sodium The cations were replaced by potassium, and the samples were prepared using traditional ion exchange methods ("zeolite molecular sieves", Chapter 7, pages 537 to 549, by D. Breck, Krieger Publishing Company, Malabar, Florida), as in Example 4 The A-zeolite exchanged by bell was synthesized into a flexible PVC formulation and tested and shown in Table 10 below. (Table 10. Preparations and properties) Ingredients. Degree of potassium exchange (mol%) Preparations |: phr) 1 2 3 4 5 PVC resin (Oxy 230) 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 Zinc Stearate (Aldrich) 0.3 0.3 0.3 0.3 0.3 Epoxidized Soybean Oil (ESO) D-81 (Henkel) 2 2 2 2 2 Oxidized Polycarp AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 * Advera ™ 40 IP 0.3 Example IB 3.9 0.3 Example IB 9.2 0.3 Example IB 39.3 0.3 -26- This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 24 1241317 A7 B7 V. Description of the invention (Example 1B_ DTS (point 76.2 0.3 16.3 ^ 丄 6 · 9 _12.0 8.8 65.1 64.8 66.5 63.6 64.3 Secondly, Xinzhou Advera ™ 401 P, a commercial type of aluminosilicate sludge, Advera ™ is a registered trademark of pQ Company. Example 11 Example 11 demonstrates the properties of Advera 401 p and Example 1B. Some of the X-exchangeable sodium cations were replaced with calcium. The samples were prepared using traditional ion exchange methods (by D. Breck, "zeolite molecular sieve," 7 Chapter, pp. 537 to 549), as in Example 4 'will be changed a Zeolite-synthesized soft ρν. The formulations were tested and shown in Table 11 below. (Table Π. Formulations and properties) Degree of component calcium exchange '(mol%) Formulation (phr) 1 2 3 4 5 6 7 8 9 PVC resin (Oxy230) 100 100 100 100 100 100 100 100 100 100 DOP (Akcros) 50 50 50 50 50 50 50 50 50 50 Aldrich 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 ES0 D-81 (Henkel) 2 2 2 2 2 2 2 2 2 2 Oxidized polyethylene wax AC629A (Allied Signal) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Advera ™ 401P * 0 0.3 Advera ™ 40IP 3.5 0.3 Advera ™ 40 IP 7.1 0.3 Advera ™ 40IP 34.0 0.3 Advera ™ 40IP 76.3 0.3 Example IB 3.5 0.3 Example IB 7.2 0.3 Example IB 35.9 0.3 Example IB 68.4 0.3 DTS (minutes) 9.6 10.0 8.9 5.8 4.3 14.6 16.5 8.6 6.2 -27- This paper standard applies to China National Standard (CNS) A4 Specifications (210 X 297 mm)

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1241317 A7 _ B7 V. Description of the invention (* For comparison purpose, AdveraTM 401 P, a commercial 4 A aluminosilicate zeolite, Advera ™ is a registered trademark of PQ Company. Example 12 The following example shows a reduction Both the zeolite crystal size and zeolite particle size have a positive effect on the dynamic thermal stability in CPVC pipe formulations. (Table 12 · Formulations and Properties) Composition · / Fruvite particle size (μ) Zeolite LOI ㈤ Zeolite average crystal Full Size (μ) Crystallinity (%) b Formulation (phr) 1 2 3 4 5 6 7 8 9 TempRite® 3114c 100 100 100 100 100 100 100 100 100 Advera 40 IP 4.4 2.3 1.2 94 1.72 Example 12A 3.7 2.0 0.4 , 2.5a 94 1.72 Example 12B 1.2 2.3 0.4, 2.0a 84 1.72 Example 12C 5.5 1.9 0.5 124 1.72 Example 12D 2.8 4.0 0.5 100 1.72 Example 12E 1.8 2.7 0.5 100 1.72 Example 12F 1.6 2.0 0.9 107 1.72 Example 12G 1.6 2.2 0.6 106 1.72 Haake DTS (minutes) 24.6 30.0 34.5 33.0 35.5 36.8 34.4 30.8d 20.6 A two-state square cloth with a large to small crystal ratio of 80/20 uses X -The degree of crystallinity with respect to the initial crystallinity measured by ray diffraction c TempRite® 3114 is a powdered CPVC pipe compound sold by BF Goodrich. D Irregular results. Example 12A is obtained at the same ratio as Example 1B. Preparation, Example 12B was prepared by spin-jet milling the material of Example 12A. The combination of Example 12C was prepared by first dissolving reagent-grade sodium hydroxide pellets (298 g) in deionized water to prepare monoaluminate acid. Sodium solution was used to prepare Example 12C, and this solution was used. -28- This paper size is applicable to @a 家 标准 (CNS) A4 specification (21GX297 public love)! ---- 1241317

, From heating to 10 ° C and slowly adding aluminum trihydrate (324g) while stirring until the soil dissolves, then the formed sodium aluminate solution is cooled to less than 75C, and an additional (1212 5 g) of deionized water, and then the solution was cooled to room temperature. Dilute 15% sodium silicate solution (903.0 g, silica / sodium oxide = 15,57 with (1510.5 g) deionized water) % By weight), the sodium aluminate solution was added to the solution with &amp; vigorous stirring during 30 knife minutes, and then homogenized for another 15 minutes. The reaction mixture was aged at 65 rc for 1 hour, then The reaction mixture was heated to 93 rc for 3 hours. Then the content was filtered, washed with deionized water and analyzed. As measured by X-ray diffraction, the product was obtained from pure zeolite Hachi Composition, and has a 1.0 sodium oxide: 丨 alumina: 2. 00 silicon dioxide chemical composition. Huang il l 2D synthesis by first using the procedure as in Example 12C above, using dissolved reagent grade sodium hydroxide Pills (307.6 g), aluminum trihydrate (2800 g) (129 00 g) Deionized water and cooling to room temperature, Example 12D was prepared by preparing a sodium aluminate solution. Dilute a 15% sodium silicate solution (792.0) with (1290.0 g) deionized water. G, silica / sodium oxide = 15, 57% by weight), the sodium aluminate solution was added to the solution with vigorous stirring over a period of 60 minutes. Then, solution A (3 1.2 g) was added to the reaction The mixture was thoroughly mixed for 15 minutes, and then the reaction mixture was heated to 93.3 ° for 5 hours. The contents were then filtered, washed with deionized water and analyzed. As measured by X-ray diffraction The product is made of pure stagnation stone A-29. This paper size is common Chinese national standard (CNS) A4 specification (210 X 29_7 public love) _ --- ----27 1241317 V. Description of the invention (composition example 1 2E is prepared by the speckle 仏 1] 0η ′ ^, ,, and shell: the same proportion as in Example 12D, and then mechanically crushed in the ball milling process. ~ By first using the dissolution reagent in Example 12C above Grade Gas Oxidation Sodium Pills) 'Ming Dihydrate (324 Gg) 〇〇 Method of cooling deionized water to room temperature 'To prepare a solution of sodium monoammonium acid Example Dilution with deionized water—Californic acid sodium ^ (820.0 g' silica / oxidation Sodium = 3 2, 62% by weight), then, solution A (2.4 g) was added to the special acid salt solution and mixed well for 15 minutes. The sodium sulfonate solution was added to the solution with vigorous stirring over a period of 30 minutes. In this solution, the reaction mixture was then heated to 93.3 ×: Result 3 蚨 The contents were filtered, washed with deionized water, dried under trace c, and analyzed. As measured by X-ray diffraction, the product is made of pure hysteresis A, and has a chemical composition of sodium oxide: J oxide name: 2⑼stone dioxide. i ^ U2G ^ ± j ^ Example 12G was prepared as follows. Take the method of dissolving the reagent-grade steel hydroxide pellets (334.0 g), Ming trihydrate (324 g) in 1000 g) of deionized water as in Example 12 (: above, and then cooling to room temperature, To prepare a sodium chain solution. Dilute a 32% sodium silicate solution (8140 g, silicon dioxide / sodium oxide di 3.2, 62% by weight) with (1100.0 g) deionized water, and then add solution A (16.0 g) to the silicon. In the acid solution and mix thoroughly for 15 minutes. Printed on 30 paper standards (CNS) A # specifications (21G_X 297 male Eding 30-1241217) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs

A7 ---------- B7 Description of the invention (28 ^^ 一 '--- Cook Y &quot; 彳 内 泮 卜 小 vigorously add sodium aluminate solution to Liu Ben solution', and then all other It was phased for 15 minutes. Then the reaction mixture was heated to 93.3 ° C and held at 3 ° C. Then the contents were filtered, added with deionized water, dried at 1000 ° C for 12 hours and Analyze. For example, using χ-ray winding, the / lead product is composed of pure zeolite A, and has a chemical composition of sodium oxide · 1 oxidation inscription: 2. 00 chemical composition of stone oxide. All of the above The samples are all at 4 ° C (4 hours), as shown in Table [2, sf is composed of a sample having a combination of small particle size and small crystal size, unlike Xing, which has a very low Example 5 of a soft pvc #] compound with a zeolite concentration and a very high plasticizer spread, and in which the size of the zeolite particles has no significant relationship with stability, this example is related to a cpvc compound. In this example (C PVC: In the formulation, the amount of zeolite added is significantly larger and there is no plasticizer. Example 1 3 The following examples show that the amount of zeolite versus a PVC The effect of light formulations. (Table 1 3 A · Zeolite-free formulations) Component product description Formulations (phr) PvC tree month purpose (〇XY 334 ,, K = 57) 〇xy Vinyls 100 Blendex 590 Exotic special products company 0.8 Kane Ace® B-3 l K eneka 12 Thermolite® 890S AT〇 Chemical Company 1.5 Loxiol® G 1 6 Henkel 0.9 Loxiol® G70S Henkel 0.6 Oxidized polyethylene 629A Allied 0.1 The amount of zeolite A shown in Table 1 3 B Added to the adjustment given in Table 1 3 A -31-This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X; 297 mm) (Please read the precautions on the back before filling this page) 1241317

Formulations 3B. Zeolite formulations and properties) | parts —y ^ 2Aa ~ ^) d 〇 13.6 _0 ^ 8 21.6 Formulations (fhir) Γ &quot;-1.2 23T 30.0 35.2 6 34.6b. 3 at 3 00 °. Dry for 4 hours to 3.8% LOI b Estimated decomposition time when the torque is 20% higher than the equilibrium state C Estimated decomposition time when the torque is 25% higher than the balanced state d Use Haake torque galvanometer At 1901: and 50 RpM, a DTS test using 60 grams of sample has been found to require dry stone, because if there is no such drying, when the formulation is extruded, it will be in 丨. At a zeolite concentration of 2 phr or higher, the molded product is held in the hand, and the water bubbles generated from the evaporation of water are sacrificed. Example 14 This example shows a dynamic heat% resistance test for a gasified poly (vinyl chloride) (CPVC) powder compound. For each test, a 3. grams zeolite sample was added to 200 grams of TempRite® 3 114 powdered CPVC. The tube is extruded into the compound, and mixed in a food processing mixer for 15 minutes. As used by the male example, 'D 2 5 3 8 -9 5 in the A STM method is stable and hot ( DTS) test method is used to perform thermal stability test of powdered CPVC compounds. DTS performance is defined as the time required to reach a fast CPVC decomposition action point and the torque increase after the equilibrium torque has been established. -32-

1241317 A7 B7 V. Explanation of the invention (%) The dynamic thermal stability test of this example was performed using a Haake ammeter at 195 or 2OC and 35 RPM on a 70.5 g sample after 3 minutes of preheating (1 minute at 10 RPM, 2 minutes at 5 RPM), each test is repeated and the reported results for each compound are the average of two or three tests. Year 14 · Mixed ingredients and properties M c 3 a in- * Bakrb LOI (%) 0 degrees (%) c 1 2 3 4 5 6 TempRite® 3 1 14 100 100 100 100 100 100 Example 1 2 A 1.99 94 1.72 Example 1 2 F 25.50 4.2 107 1.72 Example 1 2 G 25.80 4.6 106 1.72 Example 12Fa 4.90 2.26 71 1.72 Example 1 2 Ga 3.90 2.03 73 1.72 2 0) Hourly foot Haake DTS (minutes) 13.9 20.0 27.3 27.9 18.9 18.5 1 9 5 C (Haake DTS (minutes) 22.7 33.1 34.4 30.8d 31.0 3 1.2 3 Scorch in 650 ° (: under 50% steam atmosphere) Hour 6 Equilibrium water adsorption at 4 · 6 Torr c Irregular results of crystallinity measured with X-ray diffraction relative to the initial crystallinity

The McBain-Bakr test, which is already well known in the art, involves measuring the weight of the mouth σ in a controlled atmosphere of foot pressure in a controlled atmosphere, and for the test related to the present invention, 44 6 Torr Ear water vapor pressure. -33-

Claims (1)

Patent Application No. 17808 (Chinese version of Patent Application Replacement (March 1992) A B c D Patent application scope 2 3 4 «r ^ l ^ 舆 · \ r ', whether to change the content of the compaction after the amendment of this case 5 A stable functional polymer composition containing a self-chemical polymer resin and a chemical formula M2 / n0.Al203.ySi02.wH20 stabilizer for synthetic crystalline silicates, where M is a charge-balanced cation, ^ is the valence of μ and is 1 or 2, y is in the range of 2 to 5, and w Is the number of moles of hydration water per mole of the silicate, wherein the aluminosilicate has an average crystal size in the range of 0.01 to 1 micron, and an average crystal size in the range of 0.1 to 3 microns The average particle size in the range. The composition according to item 1 of the patent application scope, wherein the composition comprises a CPVC formulation or a hard PVC formulation. A% sufficient self-chemical polymer composition, comprising a self-chemical polymer tree and a stabilizer containing a synthetic crystalline silicate of the chemical formula M2 / nO.Al2〇3.ySi〇2.wH20, Where M is a charge-balanced cation, 11 is the valence of ^ 1 and is 1 or 2, y is the mole number of silicon dioxide (SiO2), and is 1.8 to 15, and w is the fragment per molecule Molar number of hydrated acid salt, wherein the silicate has an average crystal size in the range of 0.01 micrometer to 1 micrometer, and wherein the aluminosilicate includes dehydration to an aluminosilicate Steam-burned dehydrated zeolite a with a water content between 0.1% and 8% by weight of salt. The composition according to item 3 of the patent application range, wherein the zeolite does not rehydrate to a water content of more than 10% by weight based on the weight of the aluminosilicate. A synthetic crystalline aluminosilicate having a chemical formula of M2 / n0.Al2O3.ySi02.wH20, where M is a charge-balanced cation, η is the valence of M and is 1 or 2, and y is silicon dioxide (Si〇2) Molar number is 18 to 3,5, and ~ Chinese paper standard (CNS) A4 specification (210X297 mm) is applied to this paper standard AB c D 1241317 Molar number of hydrated aluminosilicate, wherein the aluminosilicate has an average crystal size in the range of 0.01 micrometers to 1 micrometer, and an average particle size in the range of 0.5 to 3 micrometers. 6. The aluminosilicate according to item 5 of the scope of patent application, which further comprises zeolite A 07. The aluminosilicate according to item 5 of the scope of patent application, further comprising a Moisture content between 0.1% and 20%. 8. The composition according to item 7 of the scope of the patent application, wherein the aluminosilicate is dehydrated to a steam-dehydrated dehydrated acid with a water content between 0.1% and 8% by weight of the aluminosilicate salt. 9. The composition according to item 8 of the scope of the patent application, wherein the aluminate salt is not rehydrated to a water content greater than 10% by weight of the aluminosilicate. w · The composition according to item 8 of the scope of the patent application, wherein the steam caustic dehydration salt has a crystallinity of not less than 50% of the initial crystallinity of the indium stearic acid salt before the steam cauterization. 11. · A method of manufacturing a synthetic crystalline aluminosilicate with a chemical formula of M2 / n0.Al203.ySi02.wH20, where M is a charge-balanced cation, ^ is the valence of M and is 1 or 2, and y is dioxide Molar number of silicon (Si〇2), and is 1.8 to 3.5, and w is the Molar number of hydrated water of the glutamate per molecule, which is modified. Good points include: (a) Cauterizing aluminum silicon with steam Water content between 0.1% and 8% by weight of aluminosilicate, but maintaining at least 50% of the initial crystallization. This paper is sized to the Chinese National Standard (CNS) A4 (210 x 297 mm). ) 7 Ίχ 3 Ίχ m 8 8 8 8 AB c D, the scope of patent application, so that the formed dehydrated aluminosilicate will not be rehydrated to a water content of more than 10% of the weight of aluminate. 12. The method according to item 11 of the patent application range, wherein the improvement further comprises generating an average crystal size having a range between 0.01 μm and 1 μm, and an average having a range between 0.5 μm and 3 μm. Particle size aluminosilicate. Μ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)