JPS5832656A - Thermoplastic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to thermoplastic polyamide compositions, and more particularly to multiphase thermoelectric polyamides containing elastic multiphase polymers with enhanced impact resistance and durability.

Many prior art techniques exist regarding improving the impact strength of polyamides. Citrus additives have been added to polyamides to improve the toughness of magnesia. Many of these additives are elastic in nature. For example, U.S. Pat. They teach that the impact strength of boriaids modified in the final rigid phase thermoplastic stage is moderately improved.This soft modifier is coated with a rigid layer and clearly Great change in toughness i″j
It's disabled.

U.S. Patent No. 4,162,505 is based on the aforementioned U.S. Patent No.! It is recognized that the polymeric modifiers of No. 1, No. 66a274 provide improved impact strength of high molecular weight polyamides, but the resulting blends do not exhibit the good flow properties necessary for injection molding operations. υ, and Ovens et al.'s core I-shell polymers with high rubber core content cannot be mixed with or dispersed in low molecular weight nylons due to the very low viscosity of nylon above its melting point;
It is taught that the resulting insufficient shear makes it difficult to disperse viscous ingredients in a fluid medium.

Another approach to the problem of improving the toughness of polyamides is given in US Pat. No. 4,174,358. The toughened polyphasic boroid can be modified by reacting with boriad or by copolymerization with a monomer containing a functional group capable of water bonding, such as a carboxy group.
This can be obtained by incorporating an elastic body. This approach has been used for acrylates, polyethylene, ethylene-propylene rubber, ethylene-propylene-diene rubber and ethylene-vinyl acetate copolymers.
ing. The resulting functionalized bulk rubber or elastomer requires very high shear in order to be finely dispersed in the boria matrix. Therefore, to be able to flow and disperse upon heating, the rubber must be soluble (i.e., "no cross-linking"). Since the rubber particles are soluble and deformable, their final size is highly dependent on the intensity of shear during extrusion and molding.It is difficult to obtain the desired fine rubber dispersion without strong shear, and control of the rubber particle size in the final molding is not easily obtained. U.S. Patent No. 4,221,879 41F consists essentially of a polyamide, and an acrylate grafted thereon with polybutadiene as a graft substrate, and a methacrylate, acrylonitrile, and/or a polybutadiene grafted thereon. Discloses a high-impact polyamide consisting of a grafted product of a mixture with an acrylic abbide monocap.The grafted shell is generally elastic in nature.Contains a rigid shell, e.g. a styrene copolymer shell. The grafted product was found to be unsatisfactory, apparently due to its poor compatibility with the polyamide.

The present invention includes 55 to 99 parts by weight of a boria matrix resin having a number average molecular weight in the range of about s, ooo-3o, oooo, and a crosslinked elastomer core of 50 to 9o, 11 t%; ~son% rigid thermoplastic polymer shell (where t'L is 100 parts shell) from about 1 to about 251 parts per part
r parts of copolymerized ethylenically unsaturated carboxylic acid monomer, about 20 to about 80 parts by weight of copolymerized styrene, about 0 to about 79 copolymerized parts of copolymerized 91- 08 furkyl acrylate or methacrylate and about 0 to about 45
There is provided a multiphase thermoplastic composition consisting essentially of 1 to 45 parts by weight of a multiphase core/shell polymer containing copolymerized acrylonitrile or methacrylate.

The expression "consisting essentially of" means that the fundamental and essential properties of the composition of the composition are such that sleep is not adversely affected by the boria matrix resin and the polyphasic core. In addition to the shell polymer, other components are present in this toughening preform to enhance the scales. .

The toughened IP1 composite boria matrix resins of the present invention are well known in the art and are generally about 5. These include semicrystalline and amorphous resins having a number average molecular weight t ranging from p00 to 3Q,000.

Preferably this molecule tFi is about 8,000 to 20,00
It is in the range of 0. Suitable polyamides include U.S. Special Fraud No. 2,071. -250, -2,071,251,
Same No. 2:130,525, Same No. 2,130,948, Same No. 2:241,522, Same No. 2,512,966
No. 2,515,606 and No. 439 21
No. 0 - Items listed in each specification are listed. This polyester resin can be produced by condensing a saturated dicarboxylic acid having 4 to 12 carbon atoms and cyabane having 4' to 14 carbon atoms in a molar amount.

Polyhexamethylene adipamide (66 nylon), polyhexamethecin azera (69 nylon), polyhexamethylene adipamide (610 nylon), polyhexamethylene dodecanoazdo (612 nylon) and baboon (p-abanocyclohexyl). ) Metandodecano abate can be opened. Bolioid resins can also be prepared by ring-opening of lactams (e.g. polycaprolactam and polylauryllactam) and condensation of ω-abanocarboxylic acids (e.g. poly-117minoundecane). Made of mahi, it can be made.2@ma'
Copolyamides prepared by copolymerization of fI: or more of the above-mentioned polymers, or of the following components can be used. Preferred polyamides are nylon 6, nylon 61
6, and a copolymer of nylon 6-nylon and nylon 6.6. Preferably, this polyamide is linear and has a melting point of 1 above 200°C. A large proportion of the composition, up to 991% by weight, can be derived from polyamide. However, preferred compositions are 55-99% weight
, and more preferably 65 to 90% by weight.

The number average molecular weight of Boriazudo is s, ooo ~ 30,000
The molecular weight is determined by end group analysis, preferably in the range Fiaooo to 20,000, to produce a polyamide composition that can be easily molded by injection or extrusion techniques.

The multiphase core I-shell polymer of the present invention is an elastomer-based composite copolymer material having a cross-linked elastomer core and a rigid thermoplastic polymeric shell. The elastomer core is a diene elastomer, an ethylene-propylene- It can be diene rubber, acrylic elastomer or polyurethane elastomer. Examples of diene elastomers include polybutadiene, polyisoprene, polychloroprene and poly(cyanobutadiene). The diene contains up to about 50% by weight of other monomers such as alkyl acrylates and methacrylates, styrene,
It can be copolymerized with a-methylstyrene, acrylonitrile, substituted acrylonitriles, hinyl ethers, hinyl ides, vinyl esters, and others. The acrylic elastic body has 50 to 9939 parts by weight of carbon atoms of 1 to 10
an alkyl acrylate having preferably 2 to 8 atoms;
0 to 40 parts by weight of other ethylenically unsaturated monomers and α1 to 5 parts by weight of polyunsaturated cross-linking monomers such as polyacrylic and polymethacrylic esters of polyols such as butylene diacrylate and dimethacrylate, trimethylol Includes propane trimethacrylate and others, vinyl acrylate and methacrylate, divinyl and trivinylbenzene and others. Grafting monomers having 2 or 70 or more additional polymerizable unsaturated groups participating in the polymerization, optionally in different proportions, may be included in an amount of from about α1 to about 5 parts by weight. can. Preferably, the grafting monomer has at least one reactive group that polymerizes at about the same rate as the other monomers, or at a slightly slower rate. The remaining reactive groups, on the other hand, polymerize at a substantially slower rate. The rate of polymerization increases, particularly during the later stages of polymerization in the elastomer core, and thus the surface TFC of the elastomer particles results in residual unsaturation levels near the surface. When a rigid thermoplastic shell is then polymerized on the surface of this elastomer, this residual unsaturated addition-polymerizable reactive group provided by the graft-bonding monomer participates in the next reaction, resulting in the polymerization of the rigid shell. At least a portion thereof is chemically bonded to the surface of the elastic body. The cross-linked elastomer core preferably has a glass transition temperature of about -25°C or less, and a good solubility parameter for the elastomer, close to that of the polymer, and polar and hydrogen bonding capabilities. It has a swelling index in the range of about 2 to 20 when measured in a solvent similar to Suitable solvents for acrylic elastomers include acetone, benzene and toluene.

Elastic cores are produced by bulk, emulsion and bath liquid methods.

The bulk mass produced by the bath process is converted to the state of an aqueous emulsion by techniques known in the art for addition polymerization of a rigid polymer shell onto it.

The rigid thermoplastic polymeric shell contains copolymerized ethylenically unsaturated monomers containing strong hydrogen bond-forming groups such as hydroxy, carboxy or primary or secondary amino groups. The content ranges from 1 to about 20% by weight. Typical monomers that may be used are carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid, fumaric acid and maleic acid, and ethylenically unsaturated dibasic acids. Monoesters of '-06 alcohol include monomethyl maleate, monohexyl maleate, monocyclohexyl maleate, monomethyl fumarate, motuptyl fumarate, and others.

Preferred carboxylic acid monomers include monoesters of ethylenically unsaturated dibasic acids and C14 alcohols, such as monomethyl, monoethyl and monobutyl maleate. As the hydroxy monomer, the above-mentioned carboxylic acid monomer α1-04 hydroxyalkyl ester, for example 2
- and droxyethyl acrylate, 3-hydroxypropyl methacrylate, di-2-(hydroxyethyl maleate), di-(2-hydroxypropyl) fumarate, and others. Abad monomers include acryl ado, methacrylide and mono-N-alkyl acrylide and methacrylamide in which the alkyl group contains from 1 to 4 carbon atoms. Containing rigid polymer shells include vinyl azun and N-vinyl succinimide (for example, N-vinyl succinimide obtained by partially deicing poly(N-vinylimide) in a grafting machine to an elastic core). and N-vinyl phthalide) and amino monomers (e.g. ethycin-4) are reacted with a multiphasic core I-shell polymer containing the corresponding copolymerized carboxylic acid monomer in a rigid shell. A copolymer of 2-ainoether acrylate, 2-a is a copolymer of 2-ainoethyl methacrylate and methyl-2-abanoethyl maleate, which can be obtained from the above method.

The comonomers for forming the thermoplastic polymer shell are selected so that the glass transition temperature of the rigid polymer is at least about 55°C. They are advantageously at least about 9.5 c@1
15/lx" q) selected to produce a soluble Hz filter, a moderately to highly polar, rigid thermoplastic polymer.

The combination of polar and hydrogen-bonding properties afforded by relatively high solubility parameters and strongly hydrogen-bonding comonomers provides a degree of compatibility of rigid thermoplastic polymers with boria-doratrix. Thus, the dispersibility of the core-shell polymer in the boria badratrix is enhanced so that a uniform dispersion of elastomer particles of approximately the same size as the initial elastomer latex is easily achieved, and the elastomer It is believed that the improvement in the impact strength of the body-derived boria can be optimized. f [Shikusha solubility parameter company at least about 10 cal”/α05, and about 16 (!
at"7 cm" or less.

The solubility parameter is conveniently determined by the intrinsic viscosity method for the soluble fraction of rigid thermoplastic polymers or by the swelling method for cross-linked polymers. For example, c 1-o B
It can be chosen from alkyl acrylates and methacrylates, styrene, vinyltoluene, alpha-methylstyrene, vinyl esters, acrylonitrile or vinylimide. Among the preferred common bases are methyl methacrylate, styrene, a-methylstyrene, acrylonitrile and methacrylatrile. When the proportion of strongly hydrogen bonded monomers is low, high proportions of polar monomers such as methyl Methacrylate, acrylonitrile or methacrylate trile increases the solubility/layer and the compatibility of the shell polymer with the polyamide matrix polymer. However, if the proportion of strongly hydrogen-bonding monomers is high, non-polar monomers such as styrene can be used as the only comonomer. Some preferred rigid polymer compositions include from about 1 to about 25 parts by weight of the copolymerized ethylenically unsaturated carboxylic acid, from about 20 to about 80 parts by weight of the copolymerized carboxylic acid, based on 100 parts by weight of the shell. Styrene, approx. 0
to about 79 parts by weight of ethylenically unsaturated carboxylic acid containing 8 fulkylacrylates or methacrylates and from about 0 to about 45 parts by weight of acrylonitrile or methacrylonitrile, styrene, 0j-0 , alkyl acrylates or methacrylates, and acrylonitrile or methacrylonitrile.Preferably, the hydroethylenically unsaturated carbons fR are monomaleates and monofumarates of 01-04 alcohols, and acrylic and methacrylic acid.

The multiphase core/shell polymer is separated from the core by known techniques convenient for forming discrete particles of rigid polymer, or rather, a shell of rigid thermoplastic polymer around an elastomeric core. It is produced by emulsion polymerization of a shell comonomer in the presence of an emulsion of an elastomer core. Emulsion polymerization of this shell comonomer on an elastomeric core is preferably carried out by coagulating from an emulsion and drying.
For a heavy polymer, the apparent bath melt viscosity of the core I-shell polymer when measured at a temperature 10°C above the melting point of the bolyaide and at a shear rate of 1 for 1000 seconds is the apparent bath melt viscosity of the bolyaide. and preferably 1 to 8 times the apparent melt viscosity of the boria
It is controlled so that the range is doubled. The temperature for measuring this apparent bath melt viscosity is 260° C. for the Nyan 6.6 composition. can be controlled by adding an allyl compound. Elastic body = allyl compound preferably has a thickness of 0.3 μt or less.
The thickness of the rigid polymer shell, calculated from the weight added to the core elastomer, is of a weight average particle diameter greater than or equal to the sintering of the core-shell particles during solidification and drying (
To prevent sintering and facilitate the formation of a uniform dispersion of the core-shell polymer in the polyamide, K is preferably at least about α025μ. Preferably, the particle diameter is from about α3 to a is in the range of about 8μ, and even more preferably it is in the range of about α4 to about α7μ so that the necessary - The proportion of flexible polymer shell is minimized.

When the elastomer core includes a butadiene or acrylic polymer prepared by emulsion polymerization, the particle size is generally within the range of about α1 to about α2μ. , m
This technique can give emulsions with larger particle sizes. However, the emulsion polymerization conditions that favor the formation of large particle sizes can cause significant damage such as creating vessel fouling and reducing the formation of a fine, uniform dispersion of multiphase core-shell polymers in the boria powder. Generally, the emulsion of a1 to a2 μ particle bubbles is agglomerated to about CL3 to cause the elastic core to become hard.
It is preferred to produce butadiene and acrylic elastomer core emulsions with large particle sizes ranging from about 0.8 microns. Agglomeration can be accomplished by any conventional means, such as by adding an appropriate amount of a water-soluble carboxylic acid or anhydride of such acid. The agglomerated r'LfI-emulsion is then stabilized by the addition of a suitable emulsifier.

Multiphase core〃The elastic core in the shell polymer has a diameter of about 50~
The amount of rigid polymer shell applied can range from about 90 parts by weight, from about 10 to about 50 parts by weight. Preferably, the amount of elastomeric core ranges from about 60 to about 80 kg and the amount of rigid polymeric shell ranges from about 20 to about 80 kg.
The range is approximately 40 parts by weight.

Polymerization of the rigid polymer shell is carried out under conditions that favor polymerization at or on the surface of the elastomeric core emulsion, such that no substantial number of new "seeds" or particles are formed in the emulsion. It will be carried out in This is generally achieved by controlling the emulsifier or initiator by 1° and controlling the addition rate of monomer, emulsifier and initiator. Preferably, no more emulsifier Fi is added after forming the core elastomer emulsion. Once the polymerization is substantially complete, the multiphase core-shell polymer can be prepared by any convenient method such as freezing, addition of a coagulating solvent such as methanol optionally containing a strong acid such as hydrochloric acid, or a polyvalent metal salt such as Coagulation is effected by addition of an aqueous solution of magnesium sulfate or aluminum sulfate. Wash the solidified emulsion thoroughly with water and remove the emulsifier and
t and dried preferably at a temperature at least about 10° C. below the glass transition temperature of the rigid polymeric shell.

The polyamide and multiphase core-shell polymers are prepared by melt-blending them in a closed system at temperatures ranging from about 5 to about 100°C above the melting point of the polyamide. Manufactured. - Axial or twin-screw extrusions can advantageously be used for this binding process. The advantage of the compositions of the present invention is that they have a single acr.
Ease of blending in the eW polishing machine and the formation of a uniform subicron dispersion of the multiphase core-shell polymer in the boria-doped f'L! It's all about how easy it is. Such an effect may be achieved if the latex particles obtained after grafting a rigid shell onto an elastic core retain their shape and size when dispersed in polyamide by melt blending. I believe that this can only be achieved by In order to achieve this, the polymer crumbs obtained by coagulation of the latex should be able to break down into particles of grafted latex. In the process, the dried crumbs are exposed to light to enable their redispersion.
It must have loose agglomerations (clusters) as much as possible. This looseness is facilitated by the rigid polymeric vinyl which prevents the elastomer particles from sintering into a single mass.

The improved toughness of the multiphase thermoplastic compositions of the present invention when compared to unblended boliabads is demonstrated by the higher notch values and the reduction in % brittle failure in the multi-axis driven dart test. nru. The Izod value increases steadily with increasing amount of elastomer core material in the thermoplastic composition, and this indicates that the elastomer wheel is 12 to 18% of the composition.
Weight % range Ω if 300-100 D, T/Il
It is within the range of 1 note. That is, a value of 500 J/m notch can be easily obtained. Negligible elastomer concentrations reduce the % brittle failure in the multi-axis driven dart test, and the % is reduced to zero when the elastomer content is 10% by weight or more. Significant improvements in impact strength are also observed when cutting at low temperatures, such as -40° C. and above.

The compositions of the invention may contain one or more conventional additives such as stabilizers and inhibitors against oxidative, thermal and UV degradation, lubricants and mold release agents, colorants, nucleating agents and plasticizers. can be denatured by Up to 50% glass fibers or fibrous and particulate inorganic fillers can substantially increase the modulus and heat distortion resistance of the bolioid composition.

Stabilizers can be included in the thermoplastic composition at any stage in its preparation. Preferably, the stabilizer is included initially to preclude initiation of decomposition before the composition is heated. Such stabilizers must be compatible with the composition. Oxidative and thermal stabilizers useful in the materials of this invention include:
Examples of general Kf materials used in polyamides, elastomers, and addition weighted materials include: Examples include cuprous halides (such as chlorides, bromides and iodides) and also sterically hindered phenols, hydroquinones, phosphites and extreme substitutes of these groups and combinations thereof. Combination fee: 11% for group metals such as sodium, potassium and lithium.
External directing agents can include extremely substituted resorcinols, salicylates, benzotriazoles, benzophenones, and others.

Suitable lubricants and type #i1 agents include stearic acid, stearic alcohol, stearamide, etc. Examples of organic dyes include nitrosine and others. Suitable pigments include titanium dioxide, cadmium sulfide, cadmium sulfide, caddobalam selenide sulfide, phthalocyanine, ultramarine blue, carbon black, and others. Suitable fibrous and particulate fillers and reinforcing agents include charcoal wood ML fibers, glass fibers, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, -silica, Examples include mica, stone, and others. nucleating agents, calcium fluoride, sodium phenylphosphinate, alkaline finely divided polytetrafluorocarbons, up to about 20% by weight, based on the weight of the composition, as plasticizers, octyl phthalate; Examples include dibenzyl tucrate, butylbenzyl ester, hydrocarbon oil, N-n-n-butylbenzenesulfonide, N-ethyl 0- and p-toluenesulfonamide, and others.

The toughened thermoplastic compositions are commonly used in the molding of thermoplastic articles, and are useful in a wide variety of shapes, including moldings, parts, and extrusions, such as tubes, films, sheets, It can be processed into tings.

The following examples illustrate the invention, in which parts and percentages are not specifically stated, and all parts and percentages are by weight.

Preparation of Elastic Lower Polymer Polybutadiene latex is prepared by polymerizing butadiene to 98% conversion using a redox initiator in 70 liters. This latex 1
- 1: having a solids content of 42% and a weight average particle size of α 15μ - 1, 1 part by weight of acetic anhydride mixed with 60 parts by weight of crushed ice for 200 parts by weight of this latex is rapidly added. Add, and to this latex' about 15
Stir vigorously for 2 seconds and leave undisturbed for 50 minutes.

Next, it is agglomerated and the next latex is "oaf".
ac) 2 parts by weight of a mixture of mono- and diphosphate esters of an alkylphenoxy polyethylene glycol having about 9 ethylene oxide units per glycol molecule sold under the name J610 (Ahyp Corporation'H Todoroki). It is then stabilized by careful addition. The emulsifier is made p by the addition of sodium hydroxide solution.
H12Kmml added as a 10% aqueous solution
Ru. The agglomerated latex is gently stirred to evenly distribute the surfactant thereon. The agglomerated latex contains 29% rubber solids. The weight average particle size of the agglomerated latex is 0.5μ.

In the same way, add α to 200 parts by weight of polybutadiene latex.
By adding 6 parts, 0.8 parts and 1.2 parts of acetic anhydride, an agglomerated polybutadiene latex with weight average particle sizes of 129μ, 14μ and α64μ is produced.

Preparation of multiphase core/shell polymer α 5 parts Weight-average particle The agglomerated latex containing 100 parts by weight of polybutadiene is heated using a temperature control device b. Two graduated holding tanks (for addition of monomer and persulfate solutions). ), placed in a reaction vessel equipped with baffles, a Teflon blade stirrer, and a condenser, and diluted with water for approximately 20 minutes.
% solids. Sparger for about 15-20 minutes
Simply replace the patch by passing 7 nK nitrogen as a bubble through it. During this time, the patch is gently agitated and brought to 80°C.

A monomer mixture containing 39 parts by weight of styrene, 18 parts by weight of acrylonitrile%, 3 parts by weight of monoethyl maleate and 75 parts by weight of terpinolene, and 90 parts by weight of berfurphate in 56 parts by weight of water. An aqueous solution of potassium persulfate is prepared.

The monomer 1 compound and nosulfate solution are charged to a holding tank and the andn are also replaced by bubbling nitrogen through for about 5-10 minutes. A nitrogen atmosphere is maintained in the vessels and tanks throughout the entire polymerization process.

Approximately 10-15% monomer/initiator charge is added to the patch once the vessel contents reach 80°C.

Agitate this patch for approximately 1'5 minutes. At the end of Jin's time,
Continuous addition of monomer and catalyst streams n is started. 2
Adjust the addition rate of each stream to complete the addition in about 4 hours and then continue the polymerization at 80° C. for 1 hour. Monocapsular body conversion is 95%. At the end of polymerization, the patch is passed through cheesecloth. Despite the fact that generally no additional curing agents are added during the polymerization process, coagulums are rarely obtained. For this latex, "Polygara" released by Niji Royal Co., Ltd.
Mixed alkali-based aryl phosphite 2 with trade name 'I'
12.5% by weight of 2,6-di-tert-butyl-4-methylphenol sold by Shell Caical Corporation under the trade name Ionol J. Add the aqueous emulsion containing.

The amounts added are determined to provide 2 parts of Polyguard and 1 part of ionol per 100 parts of polybutadiene charged. The resulting stabilized latex is 95-9
Soaked in a 3% aqueous solution of magnesium sulfate hexahydrate at 8°C.
Coagulate by adding Use 2 to 3 volumes of magnesium sulfate solution per 1 volume part of latex.

Wash the coagulated material on the filter several times with cold filtered water,
Most water is removed by vacuum filtration or centrifugation.

The remaining water is removed in an open vacuum at 60-70'C. Continue drying in the bottle so that no trace of moisture can be detected in the dry ice/acetone trap.

The ratio of the elastic core to the rigid shell is Fi1:α6. Grafting efficiency is 28%. The intrinsic viscosity of the soluble fraction of the rigid shell is α32.

The apparent melt viscosity of the multiphase polymer is 260°C and 105
&8 kilopoise (K-poi) at a shear rate of 1/sec
se). This example is listed as Example 1 in Table 1. The apparent melt viscosity of Polyamide 1 of Table 2 under the same conditions is 1.5 kilopoise.

Similarly, multiphasic core-shell polymers with different core-shell ratios and different stiffness polymer-shell compositions were prepared by selecting polybutadiene latexes of appropriate particle size by the same method. Ru.

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Grafting Efficiency of Multiphasic Core-Shell Polymers Grafting efficiency is measured by extracting the shell polymer that has no polyptaphase grafts chemically bonded or grafted to it.

The latex portion obtained at the end of the grafting process (before addition of stabilizers) is coagulated in a large excess of acidified methanol. The coagulum is washed several times on the filter with methanol and then dried at 60°C. The dried material is then compression molded into a solid sheet in a mold heated to about 150°. Note that compression molding of the crumb into a sheet is necessary to avoid colloidal dispersion of the rubber during extraction with acetone.

This compression molded sheet is cut into strips. A carefully measured weight of material (approximately 2 F) is then added to approximately 18-2
Place in acetone at about 50 hours for 0 hours, remove the clear acetone solution with a syringe and collect. This extraction operation is repeated one more time and all the collected acetone solutions are dried by solvent evaporation. The dry form of the acetone soluble material (i.e. the portion of the shell polymer that was not grafted onto the polybutadiene core) was thus obtained.
Ru.

Since the total amount of shell polymer is known, the amount of grafted shell material in the pre-weighed molded strip is calculated. Grafting efficiency is the weight ratio of the grafted shell polymer extracted with acetone to the total violet of shell polymer present in the sample.

Grafting is essential - here is the entire shell of the shell in the material, dl and we
is a replica of the extracted shell polymer.

Grafting efficiency generally ranges from about 20-40%;
The rt is then increased by decreasing the particle size of the polybutadiene core, decreasing the shell-to-core ratio, and decreasing the chain transfer agent capacity in the shell polymerization.

The intrinsic viscosity and glass transition temperature of the non-grafted portion of the multiphase core/shell polymer and the extraction of the shell polymer are determined using DMF (dimethylform''!
A raid carried out by pigeons. The crumb obtained by coagulation with MgSO4K is dried and molded into a sheet as described above, and the strip is then leached in DMv. The solution passed through a glass filter is precipitated in acidified methanol/water (80:20). Collect the precipitate, wash with methanol/water and dry.

The intrinsic viscosity of the non-gelabated shell polymer was determined by DMI at 25°C.
Measure the glass transition theory on a DuPont Differential Scanning Calorimeter Model A900 using a sample bubble of about α1 to about α2t. The heating rate is 20°C/min. Tg is the midpoint of the glass transition deflection.

Preparation of Polyand Blends The blend components are carefully dried before extrusion. The bolioxide in pellet form is dried overnight at about 80° C. at a pressure of 1 torr or less.

The separately dried nine multiphase core/shell basins are then mixed with polyamide pellets by inversion in a drying container at a temperature approximately 10° C. below the glass transition temperature of the rigid polymer shell and ready for use. Store in a sealed container.

For bath melt blending, a single stage 2.54 (xnuon) extruder with a two stage 1ift (exhaust hole plugging) 24:1 screw with a screw speed of 1100 rpm is used. have 40
Use the mesh screen in the extruder nozzle.

For nylon 6.6, the set temperature profile for the glaze stage from the hopper to the nozzle is typically 285
282°C, 277°C, 266°C and 266°C. The dried blend is charged to a nitrogen purged hopper and kept under nitrogen during the extrusion process. The extrudates are passed through a short section of water 1 2"L stream of air and hot milled in a nitrogen purged jar.

The extrudates are dried overnight at about 70° C. in a Makabe. Second
A second extrusion is then carried out. The extrudate after this second pass is again dried at 70° C. for 1 hour before molding.

Often a slightly rough extrudate is obtained in the first extrusion, probably due to the dispersion of the bulky rubber in the hopper. In the case of the second extrusion, generally smooth extrudates are obtained.

Molding of the Blend Injection molding was performed in an Arburg factory. Typical molding conditions used for the nylon, 6.6 blend ItC71 were as follows.

271℃ 26o 266 66 injection pressure
9.0~120 kPaPa light time 2~
4 seconds Hold time 15 seconds Total cycle 50-45 seconds Screw speed 2-5o to 350 rpmPolyamide and core I shell The apparent bath melt viscosity 1 was calculated using a 10:1 Cabirary length/diameter ratio to increase the polyamide melting point to 10°C.
At high temperatures, Eliegel
Mechanical properties in polyblends Polyblend samples of polyamide and multiphase core I-shell polymers were tested in a dry-as-mold (Aff-Mckelvey) rheometer.
A zero-order test is used for mechanical testing in the S-molded state.

The notch is made of izotto toughness STM D-256-5
6 Tensile strength 1i: ASTM D-638-
58T elongation ASTM D-638-5
Tensile modulus of 8T polymer ASTM D-882
Particle buoys Electron dim mirror and multi-axis drive dart tests of zecrotome sections of AMLT material were carried out using darts with a diameter of 6.35 m and a hemispherical head fired at a speed of 112 m/min. Ru. Data for Polyblend is given in Table 2. Matrix bolioid is nylon 6.6,
and nylon 6.67 nylon 6 copolymer in an 85:15 ratio with a number average molecular weight of 18,000. The IJ polymers are respectively referred to as polyamide 1 and polyamide 2 in Table 2. Examples 1 to 43 are within the scope of the present invention. Examples A-IF are included for comparative purposes. I'm here. The data for Boria Cdo shows that the notch impact strength is very low, and the impact resistance in the driven dart test is very high, and the frequency of brittle failure is significant, i.e. 10
%. Butadiene I polyamide
When blended with stycine core shell] iIO form (flJ) and hyphtadiene styrene acrylonitrile core I shell polymer (Example B% C and D),
At best, only a moderate improvement in notch impact strength is obtained, but the frequency of brittle failure in driven dart tests increases. Some improvement in impact strength and reduction in brittle failure is observed when carboxy monomers are introduced into the butadiene I-stycine core I-shell polymerization (Example X vs. Example M).
Similarly, a small improvement in impact strength is observed for core/shell polymers containing acid-modified polymethyl methacrylate as the shell polymer (Example P), in contrast, when the shell is composed of carboxy monomers and styrene. Significant improvements in notch impact strength and brittle failure rejection in the driven dart test were obtained when acrylonitrile and acrylate monomers contained methacrylate monomers and acrylonitrile and acrylate or methacrylate monomers. (Examples 1 to 43).

Examples 4-7 provide a series of blends containing core/shell polymers with reduced polybutadiene content. The notch impact strength decreases with decreasing butadiene content, but in all cases only malleable failure is observed in the driven dart test. The improvement in notch impact strength over unblended polyamide is very significant when the butadiene content is about 12% or higher.

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55 25 91634 2
XXVIi3.0 20 9223
5 2 XXI 30
20 98756 2 XX■
3ri 25 94457
2 XXW 30 20
90638 2 XXI
55 23 91139 2
XXX 50 19 9164
0 2 XXXI 30
20 80841 2 XXXI[3
020857422XXXII 30
20 82445 2 XXXIV
50 20 803 ID engineering 47 48 52
201 0 2 4 5 0 6 2 1 52 - Examples 8-13 demonstrate the effect of elastic core/rigid shell ratio and retaining the core around the soft core and comparing the size of the initial polybutadiene core. The advantages of having a sufficiently hard shell to enable the formation of a dispersion of coagulated core I-shell polymers with large sized particles are shown.

Electron micrographs show that the polyblend of Example 11 has a size similar to that of the initial agglomerated polybutadiene latex (
It contains a homogeneous dispersion of core-shell polymer particles of approximately α5μ). This polyblend has high impact strength. When the amount of rigid shell holding the polybutadiene was reduced in Examples 9 and 10, electron micrographs showed that the dispersion in the bolioid was much more incomplete, and mechanical tests showed that with a decrease in the amount of rigid shell It shows that the impact strength decreases. Even at a 1:1 core/shell ratio, multiphase core-shell polymers made from α13 particle size polybutadiene latex do not disperse uniformly in the polyamide, and this polyblend has low impact strength (Examples 12 and 15)
). In contrast, although the elastomer content of Example 8 is substantially lower than that of Examples 12 and 13,4 its notch impact strength is substantially higher.

Examples 14, 17, and 18 show that polyblends containing multiphase core-shell polymers incorporating acid monomers other than noether maleate into the rigid shell also showed improved toughness. It shows that it has a sexual nature.

Examples 15, 16, and 19-26 contain a core I-shell polymer with a shell containing varying amounts of copolymerized acid monomers. Data is.

The optimum acid concentration is in the range of about 5 to 15% by weight, and this suggests settling for a carboxy group concentration in the range of about 1.6 to about 4.8% by weight. Other advantages of modified polyamide compositions include their high impact strength at low temperatures. Table 3 lists the data obtained at -40°C.

Table 5 Notch impact 5! 1 degree Bolioid 2 Mocking 49 6~76
19 141 4920
190 3021
233 4922
201 4923 233
4524 179
4825 168
4426 136 5
527 190 6128
201 5330
152 5631
141 6352 16
8 6355 206
6535 125
5536
5243-184 57 Glass Fiber Composite A glass delicate composite is obtained by blending glass fibers with a Boria <Docor> shell multiphase polymer blend at a concentration of glass fibers of 13% by weight based on the total weight of the composite.
Ru. Data are provided in Table 4 comparing the glass fiber-reinforced 9-BORIAD 1 with a blend of BORIIDE 1 and glass fiber-reinforced core-shell polymer 1.

Composites containing core I-shell polymers exhibit greatly improved isot toughness and improved elongation without significantly sacrificing tensile strength and thermal deformation resistance.

Claims (1)

Claims: 1) A polyamide matrix resin having a number average molecular weight ranging from 55 to 9911, with a number average molecular weight essentially ranging from about 1 ooo to 30,000.
t,% and approx. a cross-linked elastic core of about 2.6% by weight and a rigid thermoplastic polymer shell (with an agarth transition temperature of at least about 35°C) of about 10% to about 50% by weight.
'L is from about 1 to about 25 parts by weight of a monotactic unsaturated carboxylic acid monomer per 100 parts by weight of the shell polymer; ,2,Wow. ~Approximately 41 o. 5 polymerized l-cs alkyl acrylate or methacrylate and from about 0 to about 45 parts by weight of copolymerized acrylonitrile (containing methacrylate). A multiphase thermoplastic composition comprising ˜451i parts. 2) At 10℃ above the melting point of boriabad and 1000
The ratio of the apparent melt viscosity of the polyamide to the apparent melt viscosity of the multiphase core I-shell polymer at a shear rate fK of sec-1 is in the range of about α1 to about '1. A composition according to claim 1. 3) The multiphasic core I shell polymer has a core with a weight average particle diameter of at least about α5μ and a core with a weight average particle diameter of at least about
A composition according to claim 1 or claim 2, having a rigid body shell number with an average thickness of μ. 4) Multiphase core/shell polymer is approximately α3゛ to approximately α8μm
Claims 1 and 11a have a core having an average particle diameter in the range □.
5) The composition according to claim 3, wherein the cross-linked elastomer core includes copolymerized butadiene. 6) The carboxylic acid monomer is acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid,
Filic acid and maleic acid 1. and itaconic acid, mesaconic acid, citraconic acid, aconitic acid, maleic acid and 7 wk acid O01 6-alcohol monoester. 7) A composition according to claim 5, wherein the carboxylic acid monomer is selected from the group consisting of 01, 4 monoalkyl maleate and fumarate; 8) a notch impact strength of at least about 3001 /m,
9) The composition according to claim 7, wherein the polyamide is nylon 6, nylon 6.6t, or a nylon 6-nylon 6.6 copolymer.・10) Boriabad is nylon 6, nylon 6.6 straddling nylon 6-nylon 6
．． 8. The composition of claim 7, which is a 6-copolymer. 11) The composition of claim 9, wherein the crosslinked elastomer core includes copolymerized rLe butadiene. 12) A composition according to claim 3, wherein the composition contains up to 50% by weight of particulate mineral filler. 13) A composition according to claim 3 containing up to 50% by weight of glass fibers. 14) The polyamide matrix resin is about a, ooo to about 2
A composition according to claim 1 having a number average molecular weight in the range of 0.000. 15) The composition of claim '5, wherein the weight average particle diameter of the core is in the range of about α4 to about 0.7μ. 16) A composition as claimed in claim 1, consisting essentially of 65 to 90 parts by weight of a boria bardo matrix resin and 10 to 55 parts by weight of a multiphase core/shell polymer. 17) A composition according to claim 3, consisting essentially of 65 to 90 parts by weight of a polyamide matrix resin and 10 to 35 parts by weight of a multiphase core-shell polymer. 8. A composition according to claim 7, comprising 65 to 90 parts by weight of a boria matrix resin and 10 to 35 parts by weight of a multiphase core-shell polymer. 19) (1) Preparing an aqueous emulsion of an elastomeric core polymer with a weight average particle size ranging from about α3 to about α8μ;
About 25 parts by weight of copolymerized ethylenically unsaturated carboxylic acid, about 20 to about 80 parts by weight of copolymerized styrene, about 0 to about 79 parts by weight of 01-C! The 8 alkyl acrylate contains methacrylate and about 0 to about 45 parts by weight of copolymerized acrylonitrile or methacrylate and has a glass transition temperature of at least about 35°C and an average thickness of at least about 0.025μ. A toughened multiphase thermal method comprising graft polymerizing the shell onto an elastomer core at a core/shell weight ratio ranging from about 9=1 to about 1:1. ! ! 20) The polyamide has a number average molecular weight in the range of about 9=1 to about 20,000.
The method described in section. 21) 10°C above the melting point of Boliabad and 1000
% boriabad and the multiphasic core I-shell polymer to provide an apparent melt viscosity ratio in the range of about [L1 to about 1 when measured at a shear rate of 1. The method according to item 19. 22) The weight average particle size of the core is about 0.4 to about α7μ
22. The method of claim 21 within the scope of. 23) Any of the preceding claims 19.20421 or 22, wherein the carboxylic acid monomer is selected from the group consisting of monoalkyl maleate and fumarate.
Method described in Crab.