KR880001627B1 - Integrated additive agent - Google Patents

Abstract

A thermoplastic organic polymer is reinforced by homogeneously blending the polymer, an inorganic filler and a surfactant with a polymerizable unsatd. Si compd and its organic compd. The surfactant comprises (a) a siloxane contg. at least one Si-bonded alkyl gp. or (b) a polyoxyalkylene compd. contg. polyoxyalkylene blocks. The polymer has enhanced hysical properties e.g. impact strength and tensile strength.

Description

Integrated additives

FIELD OF THE INVENTION The present invention relates to filler polymerizable materials, and more particularly, to integrated filler-thermoplastic polymer blends to preserve or enhance the physical properties of filled thermoplastic polymer matrices and filled thermoplastic polymers including improved impact strength. It is related with the additive added suitably.

The present invention also relates to novel integral additives which are added to the filler-thermoplastic polymer blend to provide improved processing properties to the blend, such as the low pressure required to fill the molding machine in the injection molding process. The present invention also provides a process for the preparation of reinforced or filled thermoplastic polymers having improved physical properties, and also relates to the improved filled thermoplastic polymers obtained.

Very extensive research has been conducted on the treatment of fillers or reinforcing agents for use in synthetic polymers including thermoplastic polymers such as polyethylene, polypropylene and the like. Most of these studies focus on pretreatment of fillers with coupling agents. Examples of coupling agents used for this purpose are gamma-methacryloxypropyl trimethoxy, which is described in US Pat. No. 3,663,493. Silane; Tetravinylcyclo tetrasiloxane described in US Pat. No. 3,859,247; Mercapto-propyl or glycidyl propyl trimethoxysilanes described in US Pat. No. 3,853,692; Diols composed of polyoxypropylene blocks sandwiched between two polyoxyethylene blocks as described in US Pat. No. 4,017,452; Maleic acid or methacrylic acid esters of the polyether polyols described in Belgian Kingdom Patent No. 879,092. The pretreatment of the filler requires a high shear mixing of the pulverized filler and the coupling agent, which requires a large amount of energy, time and subprocesses, both of which are economically undesirable and counter to energy saving efforts.

Integrated blending techniques (also referred to as in situ addition reactions) are widely used when a coupling agent or surface treatment agent is added to a stirred mixture of polymer and filler. However, integrated formulation requires a large amount of coupling agent or surface treatment additive, and its success depends on the specific type of filler and polymer. In addition, so far, mixing times have been considerably longer in integrated formulation techniques, since the coupling agent takes time to move, react and condense on the filler surface. See E. P Plueddemann and GL Stark, "Surface Modification. of Fillers And Reinforcement In Plastics ", Published by The Society of the Plastics Industry, Inc., 32nd Annual Technical Conference, 1977, (Sec, 4-C, pages 1-9). This document describes fatty acids, phosphate surfactants, and the like used in the paint industry, with the intention of developing a system which can be transformed into surface active additives required to be suitable for individual polymers using monobasic silane coupling agents on all fillers. The same commercially available surface active agents are mentioned. However, this document does not state that such an attempt can be successfully achieved and it can be assumed that such an attempt is still under study.

There are significant problems with the use of surfactants or wetting agents in integrated additives or in situ additives. See DE Cope, "Hydrophobic Filler Wetting A New Techique For Improved Composite Performance And Production", published by The Society of the Plastics Industry, Inc., 34th Annual Technical Conference, 1979, (Sec, 24-E, 1 to 1). 3), surfactants generally do not react chemically at the filler surface, and in practice these surfactants are prone to change and often generate pores or bubbles, and typical surfactants include sulfonates, phosphates and silicones. Oils are described. This document also states that surfactants tend to have adverse effects.

In addition, US Pat. No. 4,251,576 (columns 22, lines 22-27) describes the use of nonyl phenol / ethylene oxide condensates in the monomer filler mixture to solidify the mixture, resulting in a ruptured and cracked casting. .

DC Goel, "Effect of Polymeric Additives on the Rheological Properties of Talc-Filled polypropylene", published in February 1980, Polymer Engineering and Science, Vol. 20, No. 3, pages 198 to 201, describes polymer / filler metrics. It is described to extrude a compound containing oligomers of polypropylene, talc and polypropylene oxide twice on a single screw extruder in order to distribute the oligomer uniformly. The presence of 3% by weight of oligomers in the polymer / filler matrix from the literature provides a decrease in viscosity and also a decrease in the elasticity of the filler polymer composition, suggesting that a reduction in impact properties is possible.

Therefore, the prior art generally contraindicates the addition of surfactants to the polymer / filler formulation.

In US Pat. No. 3,471,439 to Bixler et al., Particles are coated with an organic compound having a chemical affinity for the filler surface, such as a substance having at least one ethylenic unsaturation, or at least two polymerizable ethylenic unsaturations. Finely ground unreinforced fillers are described which have particles coated with compounds having and organic radical generating compounds. The filler is then dispersed in the thermoplastic polymer and the unsaturated material is polymerized to allow the filler to bind to the polymer. The patent also discloses that saturated surface active compounds such as stearic acid, calcium stearate, and the like can be used, in particular, where these compounds can be used when the hydrogen atoms have one or more carbon atoms that can be removed by free radicals. have.

In any of the references set forth above, a mixture of thermoplastic polymers and fillers, in the form described and claimed herein, for the purpose of improving processing properties, such as pressure requirements for fillers, and preserving or improving physical properties. There is no description or suggestion of a method involving the addition of a surfactant.

It is known that various surface treatment methods using silanes and / or organic coupling agents, in particular organo-functional silanes, can be applied to the fillers for the purpose of improving the usability of the fillers in the polymer matrix. Surface treatments using coupling agents are typically applied to the filler surface in a separate process prior to incorporation of the filler into the polymer composition.

It is an object of the present invention to simultaneously perform surface treatment in a filler / polymer blending process. To date, this recipe has reduced the effectiveness of functional additives as measured by the mechanical properties of the filling composition. The inventors have found that through the integrated addition, the use of silicone surfactants as well as other non-silicone surfactants can compensate for the loss of efficacy of the surface treatment. In addition, the mechanical strength properties of certain polymer / filler compositions prepared according to the present invention were superior to those of the non-filled polymers. This has led to the elimination of undesirable and uneconomical operations such as pretreatment of particulate fillers.

Intergral blending of additives, such as organo-functional silane coupling agents, offers economic advantages including substantial time and energy savings over pretreatment fillers, and also provides simplicity and convenience. Pretreatment of the filler with additives such as coupling agents may be carried out by a high-strength mixer such as Henschel or a twin-shell blender equipped with a rotating, RPM-reinforced mixing blade to prevent flocculation. Needed. The additive must be added slowly at steady flow rate to prevent aggregation. During the pretreatment step, localized hot spots are generated at or near the high speed mixing blades of the apparatus used.

This phenomenon prevents the polymer from entering the filler because the polymer dissolves and aggregates.

When using integrated blending techniques, it is certain that the additives can disperse the filler and that the additive can be uniformly dispersed through the filler. This phenomenon prevents agglomeration. In the integrated formulation according to the invention, the additives can be added quickly (at one time) to the filler or filler / polymer mixture and gently stirred.

It is an almost unexpected advantage of the present invention that the amount of additive used may be low while maintaining the advantages of using the additive. This additive may also be formulated in situ in a processing apparatus (eg Banbury) containing the filler / polymer mixture directly in accordance with the invention prior to the fluxing step of the melt blend.

Until now, the addition of fillers to plastics has often reduced some of the useful physical properties. Therefore, additional additives were used to regain these lost properties.

The main focus underlying the present invention is the unexpected synergistic effect of using surfactants alone or in combination with unsaturated silanes and / or with unsaturated organic compounds having two or more polymerizable unsaturated groups. Is to have. Prior art using such silanes and / or unsaturated organic compounds to improve filler plastics generally required pretreatment of the filler with additives prior to mixing the filler with the plastic. Up to now, poor results have usually been obtained when all the components were integrated at the same time.

A particular advantage of the surface active agent according to the present invention is that it allows the use of simpler integrated blending techniques and allows to obtain properties comparable to or better than those obtained from "pretreatment".

The present invention provides techniques, methods, and additive combinations that allow direct blending of additives into filler / polymer compositions to improve physical properties such as impact strength, tensile strength, and the like. The present invention is a polymer; Fine grinding filler; Mill siloxane-polyoxyalkylene block copolymers, siloxanes containing at least one silicon bonded to an alkyl group having 12 or more carbon atoms, or alkyl at one end being an alkenyl group or 12 or more carbon atoms Thermoplastic organic polymers such as polyethylene and polypropylene are formulated by blending a surface active agent, a polyoxyalkylene compound containing a polyoxyalkylene block terminated by a group and terminated by an alkoxy group or a hydroxy group. It provides a novel method of strengthening.

According to the invention, the novel process also contains at least one polymerizable unsaturated group, at least one ≡SiO- group and up to 5 silicon atoms in the filler / polymer mixture to improve the physical properties of the filler polymer. Also included are methods of incorporating unsaturated silicone compounds such as polymerizable unsaturated hydrolyzable silane coupling agents and / or unsaturated organic compounds containing two or more polymerizable unsaturated groups. The present invention will be described below with particular reference to silanes of the type described above as preferred polymerizable unsaturated silicone compounds, but as described below, vinyl-polymerization having a relatively low molecular weight instead of or in addition to the above-mentioned silanes. Saturated unsaturated polysiloxane oligomers can also be used.

The present invention also provides novel integral additives used to improve the physical properties of the filler / polymer blend. The novel aggregating additives contain, in addition to the surfactants of the type described above, a silane coupling agent, ie a polymerizable unsaturated hydrolyzable silane or a polymerizable unsaturated organic compound or both.

The present invention also provides a filled thermoplastic organic polymer composition produced by using the integration additive described herein.

According to the invention, in the presence or absence of polymerizable unsaturated hydrolyzable silane or siloxane oligomers and / or polymerizable unsaturated organic compounds, the surfactant is conveniently stored at ambient temperature in a suitable mixing device such as a Hobart mixer. It is added to a mixture of filler and polymer matrix (e.g. thermoplastic polymer) to uniformly disperse the components throughout the matrix. If necessary, the surfactant and other additives can be incorporated into the filler by conventional mixing methods without performing high shear operations, or can be mixed with the polymer matrix in granular or powder form.

All these mixing processes can be carried out at a convenient time or time point in the formulation process. Surfactants may also be added at any time before, during or after formation of the polymer matrix by polymerization. In addition to the surfactant, the aforementioned silanes and / or organic compounds can be added to the coarse filler material as obtained in the mine, and such addition can be carried out before, during or after the grinding of the filler to the desired particle size. have.

Advantages of the present invention include the step of adding the surfactant and the aforementioned polymerizable unsaturated hydrolyzable silanes and / or organic compounds to the starting material before, during or after their formation or processing as indicated above. It can be done at the most convenient and economical point in the whole formulation process.

Another advantage of the present invention is that certain types of fillers, such as acids, have to be subjected to polymerizable unsaturated hydrolyzable silanes and / or organic compounds in prior art pretreatment processes such as those described in US Pat. No. 3,471,439. Or need not conform to the base form. Therefore, it has the advantage of selecting from a wide variety of polymerizable unsaturated hydrolyzable silanes and / or organic compounds.

The amount of surfactant and polymerizable unsaturated hydrolyzable silane and / or polymerizable unsaturated organic compounds used is of little importance. In the novel aggregating additives, the amount of surfactant can vary from 5 to 95% by weight, the amount of polymerizable unsaturated hydrolyzable silane can vary from 0 to 95% by weight, and the amount of polymerizable unsaturated organic compounds can be from 0 to 95%. It can vary by weight percent. The total weight of the silane and the organic compound may vary from 5 to 95% by weight. All of the above weight percentages are based on the total weight of the surfactant, silane (if present) and organic compound (if present). The amount of surfactant based on the weight of the filler may vary from 0.1% to 5% by weight. The specific amount of surfactant that will yield optimal results will vary depending on the type and amount of filler. The amount of polymerizable unsaturated hydrolyzable silane used in the methods and compositions of the present invention may vary from 0.05 to 10 PHF, preferably from 0.1 to 3 PHF. The polymerizable unsaturated organic compound may be present in an amount of 0.05 to 7 or 8 PHF, preferably 0.1 to 5 PHF.

Surfactants useful in the present invention include polysiloxanes containing at least one silicon-bonded alkyl group having at least 12 carbon atoms per molecule, which are generally represented by the following average general formula.

R ₃ SiO [R ₂ SiO] _x [R _w (C _n H _{2n + 1} ) _{2 ← w} SiO] _y SiR ₃

In the above average formula, R is a monovalent hydrocarbon having 1 to 12 carbon atoms, preferably methyl, n is an integer of at least 12, preferably an integer of 24 or less, w is an integer of 0 or 1, preferably Is 1, x is an integer of at least 1, preferably 10 or more, y is an integer of 1 or more, preferably an integer of at least 10, and R, W and n are each It can be the same or different.

One or more other surfactants useful in the present invention may each be bonded to a siloxane block, an alkyl group having at least 1 carbon atom, or an alkenyl group, and the other end to an alkoxy group, a siloxane block, or a hydroxy group. There exists a polyoxyalkylene compound which has the above polyoxyalkylene block. These surfactants are “hydrolyzable” polysiloxane-polyoxyalkylene block copolymers, such as the block copolymers described in US Pat. Nos. 2,834,748 and 2,917,480, which are incorporated herein by reference, and references herein. "Non-hydrolyzable" polysiloxane-polyoxyalkylene block copolymers, such as the block copolymers described in US Pat. Nos. 3,505,377 and 6,686,254, and British Patent Specification 1,220,471, incorporated herein by reference. These various polysiloxane-polyoxyalkylene block copolymers preferably contain 5 to 50% by weight of polysiloxane polymer and the balance contains polyoxyalkylene polymer.

Preferred classes of polysiloxane-polyoxyalkylene block copolymers are those represented by the following average general formula.

In the above average formula, R 'is a hydrocarbon group of 1 to 18 carbon atoms or an alkanoyl group of 1 to 18 carbon atoms, R is as defined above, s is an integer of 1 or more, preferably 1 to 100 T is an integer of 1 or more, preferably 1 to 100, m is an integer of 2 or more, preferably 2 or 3, and p is an integer of 2 or more, preferably 2 to 40, and R, R ', m and p may be the same or different through the same molecule.

Other polyoxyalkylene surface active agents useful in the present invention can be represented by the following average general formula.

R "O (C _m H _2m O) _p R '"

In the above average formula, R " is an alkyl group having at least 12 carbon atoms, preferably having 12 to 18 carbon atoms, an alkenyl (eg allyl) group having 2 or more carbon atoms, preferably having 3 to 18 carbon atoms, Is hydrogen, alkyl of 1 to 18 carbon atoms, or alkanoyl of 1 to 18 carbon atoms, m is as defined above and may be the same or different through the same molecule.

Particular surfactants useful in the present invention are described below as Surfactants I-VI. Useful surfactants also include polyoxys having a wide range of molecular weights in which ethyleneoxy groups and propyleneoxy groups are irregularly distributed in the molecular chain or blocks of two or more ethyleneoxy groups are linked to blocks of propyleneoxy groups. Alkylene polyols such as pollingoxyethylene glycol, polyoxypropylene glycol or polyoxyethylene polyoxypropylene glycol can be included. Liquid surfactants are preferred over solid surfactants.

Preference is given to polysiloxane-polyoxyalkylene block copolymer surface active agents. The polyoxyalkylene chains or blocks are all ethyleneoxy units or all propyleneoxy units distributed irregularly throughout the block or constituting a sub-block of ethyleneoxy units and a sub-block of propyleneoxy units or It may be composed of both units. Preferred polysiloxane-polyoxyalkylene block copolymers are copolymers having high molecular weight polysiloxane blocks.

Among the polysiloxane surfactants including polysiloxane-polyoxyalkylene block copolymer surfactants suitable for use in the present invention, the polysiloxane via the "SiC" or "SiOC" bond is not bound by the divalent oxygen of the "SiOSi" bond. The valence of the silicon not bonded by the oxyalkylene block is bonded by a monovalent hydrocarbon group having at least 1 carbon atoms, preferably 1 to 18 carbon atoms. Thus, the surface active agent does not impose any restriction on molecular coordination, and may be linear, side chain, cyclic, or the like.

The polymer matrix to which the present invention is applied includes any of rubber, resin or plastic which is usually used with filler. Examples of such polymers include natural rubber; Synthetic rubbers such as styrene-butadiene rubber; Ethylene-propylene terpolymer rubber; Urethane rubber; Polyolefins such as polyethylene, polypropylene and polyisobutylene; Poly-acrylonitrile; Polybutadiene; Copolymers of butadiene and acrylonitrile; Polystyrene; Poly (styrene-acrylonitrile); Copolymers of styrene, butadiene and acrylonitrile; Copolymers of ethylene and propylene or butene-1 or vinyl acetate or maleic anhydride; Polycarbonate resin; Phenoxy resins; Polyvinyl chloride; Copolymers of vinyl chloride and vinyl acetate or other vinyl esters; Polyvinylacetate; Linear polyester; Polyvinyl acetal; Polyvinylidene chloride; Copolymers of vinylidene chloride, vinyl chloride and acrylic acid; Poly (methyl methacrylate); Super-polyamides such as nylon; Polysulfone; Allyl resins (eg polymers of diallyl phthalate); Epoxy resin; Phenolic Resin; Silicone resin; Polyester resins including alkyd resins; Poly (vinyl acetate-vinyl chloride); Poly (vinylidene chloride); Thermoplastic polyurethanes; Thermoplastic polyhydroxy ethers; Thermoplastic polyester; Poly (vinyl chloride-maleic anhydride) and the like. Preferred polymers are thermoplastic polymers such as polyolefins such as polyethylene, polypropylene and the like. The present invention can also be used in thermosetting resins.

Fillers used in polymer matrices are known to those skilled in the art and include suitable finely divided or particulate inorganic materials. When incorporated into the polymer matrix, most fillers can be used in the form of finely divided particles. These particles may be substantially isotropic with a maximum linear dimension of 10 microns, preferably 5 microns, or in the form of a plate or needle (fiber) having a thickness or diameter of 10 microns or less, preferably 5 microns or less. It may be. Compositions containing larger particles tend to have higher abrasion to processing equipment when molten and are therefore undesirable or less desirable for this reason.

The minimum particle size of the filler particles is not critical and commonly used fillers are all suitable in this respect. Asbestos, crushed glass, kaolin and other clay minerals, silica, calcium silica, among certain fillers that may be used in the present invention; Calcium Carbonate (whiting), Magnesium Oxide, Barium Carbonate, Barytes, Metal Fiber and Powder, Glass Fiber, Refractory Fiber, Unreinforced Carbon Black, Titanium Dioxide, Mica, Talc, Cut Glass, Alumina, Quartz, Olsto Nitrate (calcium silicate), and inorganic colored pigments.

Polymerizable unsaturated organic compounds having at least two polymerizable unsaturated groups include organic compounds that do not contain any groups or components that adversely affect the action of the polymer matrix (e.g., thermoplastic polymer); Filler; Vinyl-polymerizable unsaturated hydrolyzable silane; Or other ingredients such as stabilizers, antioxidants that may be conventionally used in the matrix. Examples of suitable unsaturated organic compounds include esterdiol 2,4-diacrylate, 1,4-butylene glycol diacrylate, diethylene glycol dimethacrylate, triallyl-S-triazine-2,4,6- (1H, 3H, 5H) -trione, triallyl merate, pentaerythritol triacrylate, polycaprolactone triacrylate, m-phenylene bismaleimide, dipentaerythritol pentaacrylate, melamine triacrylate , Epoxidized linseed oil / acrylate, triacryloyl hexahydro-S-triazine, trimethylolpropane trimaliate, trimethacryloyl hexahydro-S-triazine, N, N-tetraacryloyl 1 , 6-diaminopyridine, 1,3-butylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, ethylene glycol-dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate , T Ethylene glycol, diacrylate, polyethylene glycol, dimethacrylate, polyethylene glycol, diacrylate, trimethylol propane trimethacrylate, trimethylol propane triacrylate, divinylsulfone, dicyclopentadiene, bis-allyl Glycol dicarbonate, triallyl cyanurate, acetyl triallyl citrate, divinyl benzene, diallyl phthalate, tetraallyl methylenediamine, tetraallyl oxyethane, 3-methyl-1,4,6-heptatriene, 1, 10-decamethylene glycol dimethacrylate, di-, tri-, tetra- and penta-acrylate of poly (vinyl alcohol) and the like.

In addition, the following low molecular weight polyunsaturated polymers may be used: polybutadiene oligomers, hydroxy terminal styrene-butadiene and acrylonitrile-butadiene oligomers, unsaturated polyesters, partially allylated esters of styrene-maleic anhydride oligomers, and the like. .

Preference is given to using polymerizable unsaturated organic compounds having a high level of unsaturation relative to molecular weight. Thus, tri-, tetra- and penta-acrylates of poly (vinyl alcohol) as described above, and other tri-, tetra- and penta-acrylates and methacrylates of polyols such as pentaerythritol and di Pentaerythritol) is preferred.

Vinyl-polymerizable unsaturated hydrolyzable silanes used in the present invention include at least one silicon-bonded hydrolyzable group (e.g., alkoxy, halogen, acryloxy, etc.), and at least one silicon-bonded hydrolyzable unsaturated group ( Eg vinyl, gamma-methacryloxy propyl, alkenyl, gamma-acryloxy propyl, 6-acryloxyhexyltriethoxysilane, allyloxypropyl, ethynyl, 2-propynyl, etc.), preferably Ethylenically unsaturated groups. The remaining valences of silicone not bonded to the hydrolyzable or vinyl-polymerizable unsaturated groups are methyl, ethyl, propyl, isopropyl, butyl, pentyl, isobutyl, isopentyl, octyl, decyl, cyclohexyl, cyclopentyl, benzyl, To monovalent hydrocarbon groups such as phenyl, phenylethyl, naphthyl and the like. Suitable silanes of this type include silanes represented by the following general formula:

R _a SiX _b Y _c

Wherein R is a monovalent hydrocarbon group, X is a silicon-bonded hydrolyzable group, Y is a silicon-bonded monovalent organic group containing at least one vinyl-polymerizable unsaturated bond, and a is 0 As an integer of 2 to 2, preferably 0, b is an integer of 1 to 3, preferably 3, c is an integer of 1 to 3, preferably 1, and a + b + c is 4. .

Examples of suitable vinyl-polymerizable unsaturated hydrolyzable silanes that may be used in the present invention include vinyltriethoxysilane, gamma-methacryloxypropyl-trimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltri Methoxysilane, vinyltrichlorosilane, gamma-methacryloxypropyltri (2-methoxyethoxy) silane, gamma-acryloxypropyltriethoxysilane, vinyltriacetoxysilane, ethynyltriethoxysilane,

2-프로피닐트리클로로실란 등이 있다. 실란의 실리콘-결합된 가수분해성 그룹은 충진제 중에 함유되어 있는 하이드록시 그룹과 같은 그룹 또는 물과 가수분해를 통해 반응하여 실란을 충진제에 더 강력히 결합시키는 것으로 생각된다. 또한, 분자량에 대한 불포화 그룹 수준양(율)이 높은 실란이 바람직하다. 예를들면, 펜타에리트리톨 또는 디펜타에리트리톨의 트리-, 테트라- 또는 타-아크릴레이트 또는 메타크릴레이트 유도체를 트리클로로실란 또는 테트라클로로실란과 반응시켜 분자량에 대한 불포화 그룹의 수준율이 높은 실란을 수득할 수 있다. 비교적 저분자량을 갖는 폴리실록산 올리고머 [예 : 폴리(메틸비닐실록산)테트라머]를 중합성 불포화 가수분해성 실란 대신 사용할 수 있다. 특정의 불포화 중합성 가수분해성 실란 또는 이를 위한 특정의 중합성 불포화 유기 화합물이 너무 휘발성인 경우에는, 다른 물질로 쉽게 대체할 수 있다. 휘발성이 문제인 경우에는, 또한, 실란 또는 유기 화합물을 중합체와 혼합시켜 반응시키기 전에 이를 충진제와 반응 시킴으로써 휘발성을 감소시키고 또한 문제점을 제거할 수 있다.

2-propynyltrichlorosilane and the like. The silicon-bonded hydrolyzable groups of the silanes are believed to react more strongly with the fillers by reacting with water such as hydroxy groups contained in the fillers or with hydrolysis. Also preferred is a silane having a high amount of unsaturated group level (rate) relative to the molecular weight. For example, a tri-, tetra- or ta-acrylate or methacrylate derivative of pentaerythritol or dipentaerythritol is reacted with trichlorosilane or tetrachlorosilane to give high levels of unsaturated groups to molecular weight. Can be obtained. Polysiloxane oligomers having a relatively low molecular weight such as poly (methylvinylsiloxane) tetramer can be used in place of the polymerizable unsaturated hydrolyzable silanes. If a particular unsaturated polymerizable hydrolyzable silane or a specific polymerizable unsaturated organic compound therefor is too volatile, it can be easily replaced by another material. If volatility is a problem, it is also possible to reduce the volatility and also eliminate the problem by reacting the silane or organic compound with a filler before reacting with the polymer.

Relatively low molecular weight vinyl-polymerizable unsaturated polysiloxane oligomers that can be used in place of or in addition to vinyl-polymerizable unsaturated hydrolyzable silanes can be represented by the following average general formula.

Wherein R and Y are as defined above, d is an integer from 0 or 1, e is an integer from 1 to 4, f is an integer from 0 to 3, g is an integer from 0 or 1 and e + f + g are integers of 1 to 5, and d may be the same or different in each molecule.

Oligomers falling within the scope of this general formula include cyclic trimers, cyclic tetramers, and linear dimers, trimers, tetramers, and pentamers.

Therefore, vinyl-polymerizable unsaturated silicone compounds contain 1 to 5 silicon atoms linked by “SiOSi” bonds when the compound contains multiple silicon atoms per molecule, and at least one silicon-bonded vinyl It contains a polymerizable unsaturated group, and in the case of a silane, can be hydrolyzed by at least one silicon-bonded hydrolyzable group. The valence of silicon which is not bound by a divalent oxygen atom, a silicon-bonded hydrolyzable group or a silicon-bonded vinyl polymerizable unsaturated group in a " SiOSi " bond is determined by a monovalent hydrocarbon group without vinyl-polymerizable unsaturation. Combined. Vinyl polymerizable unsaturated hydrolyzable silanes are preferred in most cases.

Preferred additive compositions include surfactants as described herein and concurrently herein by Fred H. Ancker, Arnold C. Ashcraft, Jr., Martin SM Leung and Audrey W. Ku, which are incorporated herein by reference. Applied pending patent application [name of invention: “Reinforcement Promoters For Filled Thermoplastic Polymers”] (D132 74) Reinforcement promoters as described and claimed [e.g. trimethylolpropane triacrylate (TTA), penta Erythritol triacrylate (PETA), polycaprolactone triacrylate (PCLTA), m-phenylene bismaleimide (PBM), dipentaerythritol pentaacrylate (DPEPA), melamen triacrylate (MYA), Epoxidized flax oil / acrylate (ELA), triacryloyl hexahydro-triazine (TAHT), maltemic acid derivatives of methylene-aniline oligomer (MADMA), trimethylol propane trimaleate (TTM), Trimethacryloyl hexahydro-secondary-triazine (TMHT) and N, N-tetraacryloyl 1,6-diaminopyridine (TADAP)]. Such enhancers contain at least two reactive olefinic double bonds, which enhancer is characterized in that the enhancer index P, defined by the following formula, is greater than zero.

-n (n-1) Q (e + 2) (1-2R _f ) -2.5

Where n is the number of olefinic double bonds in the enhancer, Q and e are each at least one olefinic double bond, Alfrey-Price resonance and polarity variables in the compound, and R _f is the eluted Relative flow rate of the enhancer measured by thin layer chromatography on neutral silica gel using zero xylene and di-n-butyl fumarate as standard.

Based on the total weight of the surfactant and enhancer, the amount of surfactant may range from 5 to 95% by weight and the amount of enhancer may range from 5 to 95% by weight. The resulting mixture can then be used in the organic polymer / filler mixture according to the methods described herein.

Other preferred compositions include surfactants described herein, and Fred H. Ancker, Arnold C. Ashcraft, Jr., which is incorporated herein by reference. And at least two interfacial agents, such as those described and claimed in pending patent applications [name of the invention: “Synergistic Reinforcement Promoter System for Filled Polymers” ”(D13303), filed simultaneously with this application by Eric R. Wagner. [Example: trimethylolpropanetriacrylate (TTA), triacryloylhexahydro-S-triazine (TAHT), stearic acid (SYA), tetramethacryloxypropylsilane (4GMP), trimethacryloxypropylme Methoxysilane (3GMPM), dimethacryloxypropyldimethoxysilane (2GMP2M), dimethacryloxypropyltrimethoxysilane (GMP3M), tetramethylsilicate (4M), trimethacryloxypropylmethoxysilane hydrolyzate (3GMP -H), a mixture of dimethacryloxypropyldimethoxysilane hydroazate (2GMP2M-H), methacryloxypropyltrimethoxysilane hydroazate (GMP3M-H) and tetramethylsilicate hydrolyzate (4M-H) It is included. In such further preferred compositions, (a) the two surfactant components can copolymerize with each other, and (b) at least one component is at least one reactive olefinic double bond that can be mechanically chemically grafted to the polymer. (C) one component is more adsorbed on the filler surface, while the other component is more soluble in the filler polymer, and (d) the components have a synergy greater than zero, defined by Index) has S

S = 50 (Q _A + Q _S -0.2) (1-10R _f ) (0.5- △ ² )

는 가용성 계면활성제의 힐데브란트(Hildebrand) 용해도 변수와 중합체의 힐데브란트 용해도 변수와의 차이다.Where Q _A and Q _S are the most responsive olefinic double bond alpra-Price resonance parameters among adsorptive and soluble surfactants, and R _f uses xylene as eluent and di-n-butyl as standard Relative flow rate of adsorbent measured by thin layer chromatography on neutral silica gel using fumarate,

Is the difference between the Hildebrand solubility parameter of the soluble surfactant and the Hildebrand solubility parameter of the polymer.

Based on the total weight of the surfactant combined with the surfactant, the amount of the surfactant may be in the range of 5 to 95% by weight and the total amount of the surfactant may be in the range of 5 to 95% by weight. Based on the total amount of the two surfactants, the amount of surfactant relative to each other can range from 5 to 95% by weight and the other can range from 5 to 95% by weight. The mixtures of the surfactants and surfactants obtained can be used in the organic polymer / filler combination, according to the methods described herein.

In the following description of the examples, the numerical examples are in accordance with the present invention, and the written examples are not in accordance with the present invention and are presented for comparative purposes. Unless otherwise specified, temperatures are in degrees Celsius. The following notations used in this embodiment and anywhere in the specification have the following meanings.

psi: pounds / (inch) ^2.

%:% By weight unless otherwise specified.

g: grams.

wt: weight.

parts: parts by weight unless otherwise specified.

pts: parts by weight unless otherwise specified.

pbw: parts by weight.

ppm: parts per million parts by weight.

Ft-1bs / in: Feet-lbs / inch.

in-1bs / in: inch-pounds / inch.

HDPE (0.78): High density polyethylene with a melt index of 0.78.

HDPE (0.15): High density polyethylene with a nominal melt index of 0.15.

pp: Polypropylene (Hercules, Inc., Pro-Fax 6253 PM), an isotropic homopolymer containing a proprietary stabilizer peg cage. PM stands for Pre-Mix or powder form.

pp-1: polypropylene (Hercules, Inc., pro-Fax 6501 PM), an isotropic homopolymer containing no stabilizer at all.

pp-2: Unstabilized isotropic polypropylene homopolymer sold under the trade name Vestolen p-5200.

pp-3: Highly stable isotropic polypropylene homopolymer sold under the name Vestolen-5200.

Stabilizer Concentrate XX 23: Stabilizer Concentrate of Hercules, I NC. 1.5 phr is suitable for filling pp.

ATH: Aluminum Trihydrate-In all cases, Alcoa, Inc. RH-730 grade is used. Nominal average particle size of the precipitation fillers 2μ.

ATOMITE: Calcium Carbonate supplied by Cyprus Mines, Inc. Nominal average particle size 2.5μ.

CLAY: Suprex by J.M Huber Corp. Nominal average particle size 0.3μ. Function clay.

BEAVERWHITE 200: Talc from Cyprus Mines, Inc. Nominal average particle size 7.5μ. Particle size range 0.2-70μ.

BEAVERWHITE 325: Talc from Cyprus Mines, Inc. Nominal average particle size 6.5μ. Particle size range from 0.1 to 44μ.

TALC (EMTAL 500): Vermont Talc of Engelhard Minerals, Inc. Nominal average particle size 9μ.

MICA (GRADE 200HK): Suzorite mica from Martin Marietta Resources Inc.

WOLLASTONITE (GRADE NYAD-G): 20: 1 aspect ratio calcium silicate from NYCO Products, Inc.

1/4 "CHOPPED GLASS: PPG Industries' nominal length 1/4" glass. Marked as ppg-3130.

MAPTS: gamma-methacryloxypropyltrimethoxysilane.

VTS: Vinyltriethoxy Silane

CH ₂ = CHSi (OC ₂ H ₅ ) ₃

TTA: trimethylol propane triacrylate.

Surfactant I:

Surfactant II:

CH ₂ = CH-CH ₂ -O (C ₂ H ₄ O) ₇ H

Surfactant III:

Surfactant Ⅳ:

Surfactant Ⅴ:

Surfactant VI: Tergitol primary alcohol, wherein an alcohol having 12 to 15 carbons length was reacted with ethylene oxide to obtain 7 moles of ethylene oxide per molecule.

C _12-15 H _25-31 O (C ₂ H ₄ O) _n H

Additive I: A mixture of MAPTS, TTA and Surfactant I, each having a weight ratio of 1/1/2.

Additive II: Mixture of MAPTS, TTA and Surfactant I with respective weight ratio of 1/1 / 0.3.

TTS: Isopropyl triisostearoyl titanate.

Gardner Impact: V. Abolins, G. E. Corp, Materia ls Engineering, Nov. 1973, entitled "Gardner Impact Vs. Izod ... Which is Better for Plastics?".

HDT: 264 psi .. ASTM D 648.

S ² I index: described in Monsanto Patent 3,419,517. The higher the S ² I index, the tougher the substance.

Filling pressure: The minimum injection pressure required to completely fill an ASTM molding machine so that the molding machine can be completely filled in a short time during the injection molding period. It is a measure of the ease of processing.

Charpy Impact: ASTM D 256.

PHF: parts by weight per 100 fillers.

PHR: parts by weight per 100 resins (polymer).

Pre-treated: A method of treating or coating a finely divided filler with silane or other liquid substance prior to addition to the thermoplastic.

Pretreatment (IH): IH stands for Intensive Hydrolysis. Acidified MeOH / H ₂ O is used during pretreatment with silane or other liquid material to coat the filler. Acetic acid is usually used to obtain pH 4-5.

Integral Addition: A method of simply incorporating a liquid or solid additive into a mixture while stirring the mixture of filler and polymer before, during or after the manufacture of the product, typically using a Hobart mixer for stirring. do.

[Examples 1-3 and Examples A-E]

In Examples 1, 2 and 3, gamma-methacryloxypropyltrimethoxysilane (MAPTS), trimethylol propane triacrylate (TTA) and surfactant I in an amount as described in Table 1 were mixed in a Hobart mixer. It is formulated directly into a mixture of high density polyethylene (HDPE) and aluminum trihydrate (ATH) (60% ATH based on the total weight of HDPE and ATH). The contents in the Hobart mixer are gently mixed for 10 to 15 minutes, and the resulting mixture is then melted in a Banbury mixer and molded into test pieces. In Examples 1 to 3, the additive is added directly to the HDPE / ATH blend. Measure the physical properties of the prepared specimens.

In Example A, no fillers were used, and the physical properties listed in Table I were measured for unfilled HDPE. In Examples B-E, 60% by weight ATH filler is blended with HDPE. Example B is a comparative example, no additives other than filler were used. In Examples C and D, the ATH filler was used as a Twin Shell blender [East stroudsberg Pa. The filler is pretreated with high strength formulation in combination with MAPTS and TTA in Model No. LB-S-8, manufactured by Patterson-Kelly Company, Inc., 18301. High intensity mixers are needed to prevent aggregation, and additives are added slowly at steady flow rates to prevent aggregation. Due to the high-power mixing, ie the high speed mixing blades of the apparatus used, localized hot spots are generated on or around the high speed mixing blades, so in this state the resin itself dissolves and causes agglomeration. The resin should not be added to the filler. In the integrated additions used in Examples 1 to 3, it is possible to prevent aggregation because the additive is dispersible in the filler and homogeneously dispersed throughout the filler / polymer mixture. In the integrated addition, the additives can be added to the mixture quickly, for example in one batch, without flocculation or other adverse effects. The physical properties of the test pieces formed from the mixtures of Examples B to E were measured as shown in Table I below.

The physical properties of the filled HDPEs of Examples 1 to 3 of the present invention were comparable to or superior to those of the filled polymers containing the pretreated fillers as in Examples C and D, and the S ² I index and other physical properties. In the case of the integrated addition of Example E without using the surfactant. In Example 2 representing the present invention the highest S ² I index and Izod impact were recorded. In other examples, the yield tensile strength and bending strength were recorded as the highest values in Example 2 more. It can be seen from these examples that the pretreatment of ATH filler with a mixture of MAPTS and TTA of 0.5 PHF, respectively, has superior properties compared to the non-filled HDPE and comparative compositions containing only filler without additives. In addition, the pretreatment of such ATH fillers yields an HDPE composition having superior bending strength as compared to a composition in which the same amount of MAPTS and TTA are combined and combined. The integration of MAPTS, TTA and surfactant in Example 2 yields a composition having properties that are superior to those of all other compositions obtained in these series of examples.

TABLE I

ATH Filled Polyethylene HDPE (0.78 MI)

Note: IH = strong hydrolysis (acidification MeOH / H ₂ O)

[Examples 4 to 15 and Examples F to K]

Based on the total weight of the filler and HDPE, in each case 40% of the different forms are used to prepare the high density polyethylene composition with six different fillers using fillers. The types of fillers are listed in Table II below. In each of Examples F to K, fillers are used without additives or without pretreatment and these examples are indicated as comparative examples. In each of Examples 4,6,8,10,12 and 14, Surfactant I is in an amount of 0.75 PHF, blended lightly in filler and HDPE prior to solvent treatment of HDPE to produce a melt composition. In each of Examples 5, 7, 9, 11, 13 and 15, 1.5 PHF of additive I was gently mixed with the blend of HDPE and 40% filler prior to solvent treatment to produce the melt composition. In each case, the mixture is homogeneously blended, melted and prepared into test pieces. The impact characteristics of the test pieces were measured and listed in Table II. In all cases the Gardner impact strength in Examples 4-15 was very large and in most cases was much greater than the Gardner impact strength of the corresponding comparative test piece. This result clearly shows that the composition in which the surfactant I and the additive I have been added is clearly superior to the corresponding composition in which the surfactant and the additive have not been added. In addition, in Examples 4, 6, 8, 10, 12 and 14, it can be seen that the amount of the surfactant I is at the optimum level, whereas the amount of the additive I is in most cases below the optimum level.

TABLE II

40% of various fillers in polyethylene HDPE (0.15)

0.1 PHR of Inganox 1010 and Weston 399 stabilizers, respectively, are added to each composition as recommended.

(week)

Surfactant I remained constant at 0.75 PHF.

Additive I remained constant at 1.5 PHF.

The comparative example contains only filler and HDPE (0.15).

TABLE II (CONTINUED)

40% of various fillers in polyethylene HDPE (0.15)

0.1 PHR of Inganox 1010 and Weston 399 stabilizers, respectively, are added to each composition as recommended.

(week)

Surfactant I remained constant at 0.75 PHF.

Additive I remained constant at 1.5 PHF.

The comparative example contains only filler and HDPE (0.15).

[Examples 16 to 21 and Examples L and M]

In these examples, the base composition used is polypropylene filled with aluminum trihydrate (ATH) which is 60% based on the total weight of polyflopropylene and ATH. In Examples 16-21, the surfactants of the form and amount as shown in Table III were gently blended into the ATH filler and polypropylene powder mixture to form a homogeneous blend. In Examples 17, 18, 20 and 21, 2.5 PHF of MAPTS was added together with the surfactant set in the formulation prior to solvent treatment to melt the polypropylene, and in Example 19, 0.7 PHF of MAPTS and 0.3 PHF of TTA were added. Is added with the surfactant set in the formulation.

In Example L, no additives were used in the 60% ATH polypropylene blend. In Example M, 2.5 PHF of MAPTS is added to a 60% ATH polypropylene blend. After mixing, each compound is molded into a test piece for solvent treatment to melt the polypropylene. Physical properties were measured for each test piece, and the obtained results are shown in Table III. In each case, compared to the composition of Comparative Example L, which contains no additives as a result of integrating the surfactant with or without MAPTS, improved Gardner impact strength without any adverse effect on the other physical properties listed in Table III. The composition having was prepared. As the integrated addition of the MAPTS and the surface active agent in Examples 17 to 21, when compared with Comparative Example L and Comparative Example M, in which the MAPTS is added, the Gardner impact strength without impairing any of the mentioned physical properties. Improved. In addition, the preparation of the composition containing the surfactant in Examples 18 to 21, etc., compared with Comparative Example L, in which the composition could not fill the molding machine even under a pressure of 18,980 psi, the obtained composition was used to fill the molding machine during injection molding. Improvements were made in that the required pressure could be much lower. In each case, the treatment test is performed by first treating each composition in Examples L and Examples 18-21 on a roll mill at 380 ° F. followed by injection molding. The composition in Example 20 had a high Gardner impact of 454 inches-pounds / inch, while the Gardner impact of the composition in Example M, which contained the same amount of MAPTS but did not contain surfactant, was 71 inches-pounds / inch. Have The S ² I index and the Izod impact strength of the compositions in Example 19 were superior to any of the compositions in this series of examples.

TABLE III

60% ATH Filled Polyethylene PP ^*

*: Xx23 stabilizer concentrate of 1.5 PHR is added to each composition as recommended by the manufacturer.

[Examples 22 to 32 and Examples N to P]

For each of these examples, except Examples 22 and 27, the amounts of MAPTS described in Table VI were mixed by gentle stirring in polypropylene and polypropylene mixed with 60% by weight aluminum trihydrate based on the total weight of ATH. do.

In Examples 22-32, Surfactant I in the amounts described in Table VI were also gently mixed with the 60% ATH-polypropylene mixture. After sufficient mixing, each mixture is solvent treated, melted in Bratender Torque Rheometer, and pressed into specimens. For each test piece, the Gardner impact strength test was carried out and the results are shown in Table VI. The results described in Table VI show that in each case using equivalent amounts of MAPTS, compositions that also contain surfactant I contained an equivalent amount of MAPTS, but surfactant I was much better in Gardner impact strength than compositions that did not contain surfactant M. Indicates. Comparing Example N with Example 24, the Gardner impact strength of a small amount of Surfactant I, on the order of 0.5 PHF, was nearly doubled.

Comparing Example 25 with Example P, Gardner impact strength could be more than doubled by the use of 0.5 PHF of Surfactant I at 2 PHF levels of MAPTS.

Table IV

60% ATH Filled Polypropylene PP ^*

* 1.5 PHR xx23 stabilizer concentrate in each composition

[Examples 33 and 34 and Examples Q to S]

In these examples, 70% potassium carbonate filler is blended with polypropylene. No additives were added in Example Q. In the remaining examples, 2.6 PHF of MAPTS was integrated in the polypropylene-calcium carbonate blend. In addition, in Examples 33 and 34, the 0.5 PHF surfactants listed in Table V were integrated in the calcium carbonate-polypropylene blend. In Example S, TTS of 0.5 PHF is integrated in the calcium carbonate-polypropylene blend. As seen in Comparative Example Q, incorporation of 70% calcium carbonate results in a composition that is difficult to advance injection molding due to high pressure filling requirements. The incorporation of MAPTS and TTA does not improve the manufacturing process as can be seen from the filling pressure requirements of Example R. In the case of integrated incorporation of TTS, only very small filling pressure requirements have been improved, but little improvement has been made in the S ² I index or the Izod impact. As can be seen in Examples 33 and 34, the integrated formulation of the surface active agent greatly improved the filling pressure requirement, and compared to Q and R in the implementation, the Gardner impact as well as the Izod impact were increased and a very high S ² I I could get the index. Only the composition of Example 33 was a composition showing yield tensile strength indicating the elastic component of the composition.

The compositions of Examples 33 and 34 increased from 71% to 77% compared to only 9% improvement in TTS (Example S) in burst tear strength. The compositions of Examples 33 and 34 had an increase in flexural strength of 54-61% compared to the composition of Q in the comparative example and the TTS composition of Example S was nearly improved.

In addition, the compositions of Examples 33 and 34 showed an increase of 87% and 97% in izod impact strength compared to the comparative composition, whereas the Izod impact strength was the same or lower in the TTS composition. In Gardner impact strength, the compositions of Examples 33 and 34 were 164% and 239% higher, respectively, compared to Comparative Example Q.

The results in Table V show that the best properties can be obtained with the compositions of Examples 33 and 34.

TABLE V

70% CaCO ₃ (Automite) Filled Polypropylene PP ^*

* 1.5 PHR xx23 stabilizer concentrate was added to each composition.

** Injection molding conditions are 450 ℉ each for three-band barrel temperature, 150 ℉ for molding machine

Example 35 and Examples T and U

The mixture is mixed melted in a Banbury mixer to prepare three composition blends from 70% calcium carbonate and polypropylene based on polypropylene and calcium carbonate weight. To the formulation of Example U and Example 35, MAPTS of 0.11 PHF and TTA of 0.11 PHF are added in aggregate. In addition, the formulation of Example 35 is integrated with 0.21 PHF of Surfactant I. These formulations are processed in a Banbury mixer, followed by injection molding each formulation to prepare test pieces. Physical properties were measured and listed in Table VI. The test piece of Example 35 showed more than three times the Gardner impact strength than the comparative example T test piece, and showed a higher impact strength than the test piece of Example U. In addition, the yield tensile strength and burst tensile strength for the composition of Example 35 showed higher values in Examples T and U.

Table VI

70% CaCO ₃ (Automite) Filled Polypropylene PP ^**

* 1.5 PHR xx23 stabilizer concentrate was added to each composition.

[Examples 36 to 41 and Examples V and W]

The compositions of these examples are prepared from 40% of clay (Suprex) and polypropylene based on the total weight of polypropylene and clay. No further additives are added to the composition of Example V. In Examples W and Examples 36-41, TTA of 5.0 PHF is integrated into the composition in a Hobart mixer. In each of Examples 36 to 41, the surfactants shown in Table VII are added in 0.5 PHF and each composition is mixed to obtain a homogeneous blend. Thereafter, these compositions are melted to prepare test pieces. The physical properties of the test pieces were measured and listed in Table VII. From these results, it can be seen that by adding the surfactants in Examples 36 to 41, the filling pressure of the formulations is greatly reduced compared to the formulations of Examples V and W without addition of the surfactants. In addition, the compositions of Examples 36-41, where this fill pressure requirement is greatly reduced, do not significantly compromise other physical properties.

[Table VII]

40% Clay (SUPREX) Filled Polypropylene PP ^*

* 1.5 PHR xx23 stabilizer concentrate and 1.0 PHR Araldite 7072 stabilizer were added to each composition.

** Molding machine temperature. 100 ° F barrel temperature (3 bands: front, center, rear) at 450 ° F.

Example 42 and Examples X and Y

Three formulations are prepared from polypropylene powder and 40% talc (Beaverwhite 325) and a stabilizer of about 1.5 PHR shown in Table VII. Based on 60 parts by weight of polypropylene in the formulations of Examples Y and 42, 0.68 parts of VTS is added to each formulation, and in Example 42, 0.33 parts of surface active agent I is added based on 60 parts by weight of polypropylene. do. Each mixture is thoroughly blended, melted and injection molded under the conditions given in Table VII.

The filling pressure requirements for each formulation are shown in Table V, which clearly shows that the filling pressure requirement of the formulation of Example 42 is significantly lower than any of the other two formulations.

[Table VII]

Filling pressure of 40% talc (BEAVERWHITE 325) filled polypropylene

* 1.5 PHR stabilizer concentrate xx23 is added to each composition.

** During the next injection molding condition.

3-band barrel temperature, ℉: 500, 500, 500

Molding Machine Temperature ℉: 115

Example 43 and Examples AA and BB

In each of these examples the formulation is prepared from the polypropylene, talc and stabilizer concentrates in the amounts given in Table IX. In the blend of Example BB and Example 43, 2.5 parts by weight of MAPTS is added, and in Example 43, 0.5 parts by weight of Surfactant I. Each formulation is processed in a Banbury mixer and injection molded under the conditions specified in Table IX. Fill pressure requirements for each formulation were measured and listed in Table IX. Fill pressure requirements for the formulation of Example 43 were significantly lower than for each of the other two formulations.

[Table VII]

Filling pressure for tabbing (BEAVERWHITE 200) filled polypropylene

* Under the following injection molding conditions;

3-band barrel temperature ℉: 450, 450, 450

Molding Machine Temperature ℉: 115

[Examples 44 to 46 and Examples CC to EE]

The blend is prepared from 100 parts by weight of polypropylene and 100 parts by weight of calcium carbonate as described in Table X.

Also added to the blend of Examples 44-46 is 2 parts by weight of additive II. All formulations are thoroughly mixed using the mixing cycles described in Table X. Each of the blends of Examples 44-46 containing additive II had much higher yield tensile strength, flexural yield strength and izod impact strength than the corresponding blends of Examples CC-EE containing no additive II. The results given in Table X also show that mixing cycle 3, which involves mixing at high speed in the melt and for 60 seconds after melting before discharging, provides the best Gardner impact strength without compromising other properties. Is showing.

Table X

50% CaCO ₃ Filled Polypropylene (Unstabilized)

Note: Mixing Cycle 1- Mix the composition at high speed in the molten state, followed by 30 seconds at low speed.

The composition melt is discharged.

Mixing Cycle 2-Composition is mixed at high speed in the molten state, and mixing is continued at high speed for 30 seconds, and then discharged.

Mixing cycle Same as Mixing Process 2, except mixing for 3-30 seconds. Then drain.

[Examples 47 and 48 and Example FF]

Three formulations are prepared from 100 parts by weight of polypropylene and 100 parts by weight of calcium carbonate. To the formulations of Examples 47 and 48 are added 0.5 PHR and 1.0 PHR of Surfactant I, respectively. Mixing cycle 2 described in Table X is used for each formulation and each formulation is molded into test pieces. After exposure to room temperature, Gardner impact strength is measured, as well as 16 hours of exposure at 2 ° F (-17 ° C), followed by testing to determine Gardner impact strength. From the results given in Table XI, it can be seen that the Gardner impact strength for the formulations of Examples 47 and 48 containing Surfactant I showed a much better improvement than the formulation containing no Surfactant. The Gardner impact strength for the formulation of Example 48 is particularly surprising because it is at least four times the Gardner impact strength of the Example FF formulation containing no surface active agent, and exceeds the capabilities of the test apparatus. The formulation of Example 48 is also particularly surprising because the Gardner impact strength after prolonged exposure to a low temperature of 2 ° F. is more than seven times greater than that of the Example FF formulation above 208 inches-lbs / inch.

TABLE VII

50% CaCO ₃ Filled Polypropylene (Unstabilized)

Note: Mixing cycle 2 is listed in Table X.

* The minimum value cannot be obtained due to the limitation of test equipment and the toughness of the composition.

Examples 49-60 and Examples GG and HH

A combination of polypropylene and calcium carbonate having the components and component contents set forth in Table XII is prepared. To this formulation is added the amounts of Surfactant I and / or Additive I and / or II in the amounts shown in Table XII and 0.2 PHR of glacial acetic acid is added in Example GG. In these examples, the Charpy impact strength was measured, and the measured values are shown in Table XII. Examples 49-54 illustrate the improvement of the Charpy impact strength as the amount of Surfactant I or Additive I increases. Example GG illustrates that glacial acetic acid adversely affects the physical properties of the composition. Examples 56 to 60 illustrate that the beneficial effect is obtained by the addition of surfactant I or additives I and / or II. The test piece of Example 56 was not destroyed in the Charpy impact test, whereas the average Charpy impact strength in Example HH was 22 feet-pounds / inch.

Similarly, in the compositions of Examples 59 and 60, four of the five specimens were not destroyed and the fifth specimen was also destroyed at a higher value than the average of four specimens prepared from the Example HH formulation.

TABLE XII

50% CaCO ₃ Filled Polypropylene

1. All five specimens are not destroyed.

2. Only one specimen is not destroyed.

3. Four specimens are not destroyed. One specimen is 34.

4. Four specimens are not destroyed; One specimen is 29.4

[Examples 61 to 69 and Examples II to NN]

These examples produce a combination of highly stabilized polypropylene and calcium carbonate in the form and amount specified in Table XIII. In Examples 61-68, the amounts of Surfactant I are added to each formulation in the amounts specified in Table XIII. In Example 69, 0.5 PHR of Surfactant IV is added to the formulation. Each blend is sufficiently mixed, melted and molded into test pieces. The physical properties of each test piece of the formulation were measured and listed in Table XIII. Examples 64 to 66 as well as Examples 62 and 63 also show an improvement in the Charpy impact strength obtained by increasing the amount of Surfactant I.

Example 63 demonstrates that the Charpy impact strength of formulations containing 0.7 PHR of Surfactant I is superior compared to Example HH without Surfactant. In addition, when comparing Example 66 to Example KK, Example 67 to Example MM, Example 68 to Example NN, and Example 69 to Example KK, as shown in the data given in Table XIII, It can be seen that the chaff impact strength was improved by using the surface active agent.

TABLE VIII

CaCO ₃ Filled Polypropylene

* 4 specimens are not destroyed and one specimen has a value of 29.

TABLE VIII (CONTINUED)

CaCO ₃ Filled Polypropylene

Three of the five specimens are not destroyed.

** Breakpoint in yield.

Example 70 and Example 00

In Example 70, 3 g of Surfactant I is added dropwise to 1500 g of relatively large particle aluminum trihydrate that is being milled in a Ball Mill mixer. In Example 00, 1500 g of aluminum trihydride of the same type is ground in a ball mill mixer. In each case, after 9.5 hours of grinding, the aluminum trihydrate was accumulated in one end of the aluminum trihydride of Example 00, but the aluminum trihydrate treated with the surfactant I in Example 70 was still free flowing. After 12.5 hours, the treated aluminum trihydride of Example 70 continues to flow freely. This example illustrates the advantages obtained by adding a surfactant while grinding relatively coarse mineral fillers into fine particles suitable for use in blending thermoplastics. Example 70 also describes a test method for a surfactant for use in the present invention. When other additives are used, including polymerizable unsaturated silanes and polymerizable unsaturated organic compounds, they may also be added in the milling step in which the mineral filler is ground to a fine particle size suitable for use as a filler in thermoplastics.

[Example 71 and Examples PP to UU]

In these examples, the formulations are prepared using high density polyethylene and ATH in the amounts described in Table XIV.

In Example PP, ATH was pretreated with 1% TTA based on the filler weight. In Example UU, ATH was pretreated with 1% MAPTS based on the weight of the filler. In Examples QQ to TT, pretreatment was carried out with the relative amounts of TTA and MAPTS in which ATH was specified in Table XIV. In each case, pretreatment is carried out by suspending ATH and additives to a high-strength mixture, such as Henschel or a bicomponent blender with a rotating high rpm powerful mixing blade to prevent aggregation. Additives are also added slowly at normal flow rates to prevent aggregation. In Example 71, 0.5% MAPTS, TTA, and Surfactant I, each based on the weight of the filler, were mixed in a powdered ATH and polypropylene in a Hobart mixer using a wired mixing blade. Integrate into the mixer. Pretreated ATH of Examples PP to UU is also mixed with polyethylene in a Hobart mixer. All mixtures are then solvent treated on a roll mill at about 365 ° F. The formulation of Example 71 during solvent treatment was found to have somewhat reduced melt flow as compared to the formulations of Examples PP to UU (measured visually). After each blend was solidified to room temperature, the solidification blend of Examples PP-UU was relatively easy to break with a hammer. However, the solidifying formulation of Example 71 was nearly impossible to break with a hammer. This example is intended to confirm the improved impact properties obtained by the integrated addition of surfactants, polymerizable unsaturated silanes and polymerizable unsaturated organic compounds.

The physical properties of the test specimens of Example RR and Example 71 were measured and described as Examples C and 2 in Table 1, respectively.

TABLE IV

* Based on filler weight.

Claims (1)

(1) enhancers, characterized in that they have at least two reactive olefinic double bonds, and the enhancer index p, defined by the following formula, has a value greater than zero, and copolymerizes with each other, wherein at least one component is incorporated into the polymer: Contain at least one reactive olefinic double bond that can be chemically grafted, one component adsorbed more strongly on the filler surface, while the other component is more soluble in the filler polymer, and the components are Two surfactants having a Synergy Index S greater than 0 (the amount of these two surfactants, based on their total weight, may range from 5 to 95 weight percent and the other 5 5 to 95% by weight (based on the total weight of the mixture) selected from the group consisting of; And (2) a siloxane containing at least one silicon-bonded alkyl group having at least 12 carbon atoms, or one end each being bound to a siloxane block, an alkyl group having at least 12 carbon atoms, or an alkenyl group, The other end consists of a mixture of 5 to 95% by weight (based on the total weight of the mixture) of a surfactant consisting of a polyoxyalkylene compound having one or more polyoxyalkylene blocks attached to an alkoxy group or a hydroxy group An integrated additive for improving the physical properties of a thermoplastic organic polymer filled with an inorganic filler, characterized by the above. P = n (n-1) Q (e + 2) (1-2R _f °) -2.5 S = 50 (Q _A + Q _S -0.2) (1-10R _f °) (0.5- △ ² ) Wherein n is the number of olefinic double bonds in the enhancer, Q and e are the Alfrey-Price resonance and polar variables of at least one olefinic double bond in the compound, respectively, and R _f ° is the relative flow rate of the enhancer or adsorbent surfactant measured by thin layer chromatography on neutral silica gel using xylene as eluent and di-n-butylfumarate as standard waterline, where Q _A and Q _S are adsorptive and Alfrey-Price resonance parameter of the most reactive olefinic double bond among soluble surfactants,

Is the difference between the Hildebrand solubility parameter of the soluble surfactant and the Hildebrand solubility parameter of the polymer.