KR100948122B1 - Chemical composition and process - Google Patents

Abstract

The present invention provides a thermally unexpanded thermal system comprising about 0.1 to about 50 weight percent of at least one inhibitor selected from the group consisting of acids having melting points below 200 ° C. and precursors thereof, and a thermoplastic polymer shell encapsulating the propellant. It relates to a solid powder composition comprising microspheres that are expandable. The present invention further relates to the manufacture and use thereof, to compositions comprising the polymer resin, to the preparation thereof, to processes for processing the polymer resin, and to the materials obtainable thereby.

Description

Chemical composition and process {CHEMICAL COMPOSITION AND PROCESS}

The present invention relates to solid powder compositions comprising microspheres and inhibitors and processes for their preparation. The invention further relates to the use of the composition, to the composition comprising the polymer resin and to the preparation thereof, to the process for processing the composition and to the objects obtainable thereby.

Thermally expandable microspheres comprising a thermoplastic polymer encapsulating the propellant can be used as blowing agent when processing the polymeric material, for example by extrusion or injection molding. However, at long process times and / or high process temperatures, microspheres can cause discoloration of the material. In some cases, there is also a problem of poor molding filling, in which an uneven surface of the shaped object is created.

In addition, pre-expanded thermoplastic microspheres can be used when processing polymeric materials to reduce density or improve texture. However, in this case, there may also be a problem of discoloration.

U. S. Patent No. 6582633 discloses that discoloration in high temperature molding can be lowered using microspheres, where the polymer shell has a high content of nitrile containing monomers.

 Numerous materials have been disclosed in the literature for reducing discoloration of polyacrylonitrile rotating solutions in dimethyl formamide, for example, BA Marien, "Stabilisation of High Nitrile Polymers. I. Effect of Dienophilic Compounds", Journal of Polymer Science : Polymer Chemistry Ed., Vol. 17., p. 425-433 (1979); D. C. Gupta et al, "Inhibition of Discoloration in Acrylic Polymers", Journal of Applied Polymer Science, Vol. 39, p. 1821-1826 (1990); And K.V. See Datye et al, "Discolouration in Acrylic Fibers, Synthetic Fibers, Jan./March 1984, p. 6-14.

US 2661347 discloses the use of maleic acid and maleic anhydride to reduce discoloration of polymers of acrylonitrile. Preferred implementations relate to the use of solvents or plasticizers for acrylonitrile polymers.

U. S. Patent 3984499 discloses the inclusion of half esters of maleic acid or fumaric acid in a nitrile resin.

US Patent 3907932 discloses the inclusion of organotin maleate compounds in the polymer composition of olefin nitriles.

EP 1471105 and WO 2005/023920 disclose the use of microspheres in combination with chemical blowing agents, which may include citric acid.

It is an object of the present invention to provide a microsphere composition that can be used to process polymeric materials at high temperatures without causing unacceptable discoloration and having satisfactory results.

Another object of the present invention is to provide a process for processing polymeric resins using expanded or thermally expandable microspheres as additives.

Yet another object of the present invention is to provide a composition comprising a polymer resin that can be used to produce a lightweight object.

It has been found that the mixing of microspheres with certain inhibitors significantly reduces discoloration when used as blowing agent in the processing of polymeric materials at long process times and / or at high temperatures.

Accordingly, one aspect of the present invention provides a thermoplastic polymer shell encapsulating about 0.1 to about 50 weight percent of at least one inhibitor selected from the group consisting of acids having a melting point of less than about 200 ° C. and precursors thereof, and a propellant. A solid powder composition comprising expanded or unexpanded thermally expandable microspheres having said acid is not citric acid.

Another aspect of the present invention provides a pharmaceutical composition comprising an expanded or unexpanded thermally expandable microspheres comprising a thermoplastic polymer shell encapsulating a propellant, wherein the expanded or unexpanded thermally expandable microspheres are selected from the group consisting of acids having a melting point of less than about 200 ° C. and precursors thereof. To a process for the preparation of a composition comprising mixing with 0.1 to about 50% by weight of at least one inhibitor. The acid is not citric acid.

Another aspect of the invention relates to the use of the composition as a blowing agent in the processing of polymeric resins.

Another aspect of the invention is selected from the group consisting of polymer resins, expanded or thermally expandable microspheres comprising thermoplastic polymer shells encapsulating propellant, and acids having melting points below about 200 ° C. and precursors thereof And, based on the expandable microspheres, about 0.1 to about 50 weight percent of at least one inhibitor, wherein the acid is not citric acid.

Another aspect of the invention is a drug selected from the group consisting of expanded or unexpanded thermally expandable microspheres comprising a thermoplastic polymer shell encapsulating the propellant and acids having melting points below about 200 ° C. and precursors thereof. To a process for the preparation of a composition comprising mixing 0.1 to about 50 weight percent of at least one inhibitor with a polymer resin, wherein the acid is not citric acid.

Another aspect of the invention is an expanded or unexpanded thermally expandable microsphere comprising a polymeric resin composition as described above, ie, a polymeric resin and a thermoplastic polymer shell encapsulating a propellant, mixed therein And from about 0.1 to about 50 weight percent of at least one inhibitor based on a microstructure, selected from the group consisting of acids having a melting point of less than about 200 ° C. and precursors thereof. And the acid is not citric acid.

Another aspect of the invention relates to a product of an optionally foamed polymeric material obtainable by the aforementioned resin processing process comprising the step of expanding the expandable microspheres.

Thermally expandable microspheres are known in the art and are described, for example, in US Pat. Nos. 3615972, 3945956, 5536756, 6235800, 6235394 and 6509384, European Patent 486080, It is described in detail in Unexamined-Japanese-Patent No. 87-286534 and WO 2004/072160. In microspheres, the propellant is usually a liquid having a boiling temperature not higher than the softening temperature of the thermoplastic polymer shell. Upon heating, the propellant evaporates to soften the shell and at the same time increase the internal pressure, resulting in significant expansion of the microspheres, usually about 2 to about 5 times the diameter of the microspheres. The temperature at which expansion begins is called T _start , while the temperature at which maximum expansion is reached is called T _max . When the T _max was exceeded, the propellant was released through the polymer shell to the extent that the microspheres began to collapse.

Expanded microspheres, sometimes referred to as pre-expanded thermoplastic microspheres, are, for example, by expanding the expandable microspheres as described herein to a particle diameter that is 2 to 5 times larger than the diameter of the unexpanded microspheres. Can be obtained. The density of the expanded microspheres can be for example 0.005 to 0.06 g / cm 3. Expansion is performed by heating the expandable microspheres to a temperature above T _start . The density of the expanded microspheres can be controlled by selecting the heating temperature and time. The expansion can be effected by means of suitable heating means in a suitable apparatus, for example as described in EP 0348372, WO2004 / 056549 or WO2006 / 009643.

According to the invention, the microspheres may be expanded, expandable, or a mixture of expanded and expandable microspheres.

The microspheres preferably have a polymer shell made from a mono- or co-polymer obtained by polymerizing ethylenically unsaturated monomers. Monomers include, for example, nitrile-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile or crotonitrile; Acrylic esters such as methyl acrylate or ethyl acrylate; Methacrylic esters such as methyl methacrylate, isobornyl methacrylate, ethyl methacrylate or hydroxyethyl methacrylate; Vinyl halides such as vinyl chloride; Vinylidene halides such as vinylidene chloride; Vinyl pyridine; Vinyl esters such as vinyl acetate; Styrenes such as styrene, halogenated styrenes or α-methyl styrene; Dienes such as butadiene, isoprene and chloroprene; Unsaturated carboxylic compounds such as acrylic acid, methacrylic acid and salts thereof; Or other unsaturated monomers such as acrylamide or N-substituted maleimides. Mixtures of the abovementioned monomers may also be used.

The present invention provides nitrile monomers for thermoplastic polymer shells of expandable microspheres, preferably in large amounts, for example from about 40 to 100%, preferably from about 60 to 100% by weight of the monomers polymerized into the polymer shell. It is particularly advantageous if it contains a containing monomer. The amount of nitrile containing monomer may also be about 80 to 100%, most preferably about 90 to 100%, in particular about 95 to 100% by weight of the monomer polymerized into the polymer shell.

The nitrile containing monomers used in the polymer shell are preferably mainly selected from one or more acrylonitrile and methacrylonitrile. If other ethylenically unsaturated monomers are present, the ethylenically unsaturated monomers are preferably selected from one or more acrylic esters or methacrylic esters. It is also most preferred to use only non-halogen containing monomers.

The softening temperature of the polymer shell, which usually corresponds to the glass transition temperature (T _g ) of the polymer shell, is preferably in the range of about 80 to about 200 ° C, most preferably in the range of about 115 to about 200 ° C.

Monomers for polymer shells may contain one or more divinyl benzenes, ethylene glycol di (meth) acrylates, di (ethylene glycol) di (meth) acrylates, triethylene glycol di (meth) acrylates, propylene glycol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, triallyl formal tri (meth) Acrylate, allyl methacrylate, trimethylol propane tri (meth) acrylate, tributanediol di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600(Meth) acrylate, it may be sometimes desirable to include a crosslinking multifunctional monomers, such as 3-acryloyloxyethyl glycol monoacrylate, triethylene acrylic formal, triallyl isocyanate, triallyl isocyanurate.

Preferably the polymer shell constitutes from about 60% to about 95%, most preferably from about 70% to 85% by weight of the total microspheres. If present, the crosslinking multifunctional monomer preferably comprises from about 0.1 to about 10 weight percent, most preferably from about 0.1 to about 1 weight percent, particularly most preferably from about 0.2 to about 0.5 weight percent of the total amount of monomers for the polymer shell. Configure.

Propellants are usually liquids with a boiling temperature not higher than the softening temperature of the thermoplastic polymer shell, and are n-pentane, isopentane, neopentane, cyclopentane, cyclohexane, butane, isobutane, hexane, isohexane, neohexane Hydrocarbons such as heptane, isoheptane, octane, isooctane, isodecane, isododecane, or mixtures thereof. In addition to these, other hydrocarbons, such as petroleum ether or chlorinated or fluorinated hydrocarbons such as methyl chloride, methylene chloride, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, trichlorofluoromethane, perfluorinated hydrocarbons, and the like. Types can also be used. The boiling point at atmospheric pressure may be within a wide range, preferably from about −20 to about 200 ° C., and most preferably from about −20 to about 150 ° C. The propellant has a boiling point or at least 50 ° C., more preferably at least 60 ° C., most preferably at least 70 ° C., but preferably is required to evaporate at least 50% by weight, preferably at least 80% by weight, of propellant at atmospheric pressure. It is particularly preferred to have a boiling range of temperatures not higher than about 150 ° C. Propellants suitably comprise about 5 to about 40 weight percent of microspheres.

In an embodiment, the propellant preferably comprises isooctane in an amount of at least 50% by weight, preferably at least 55% by weight, more preferably at least about 60% by weight, most preferably at least about 70% by weight, or If possible, it is more substantially composed of isooctane. The propellant may further comprise one or more butanes, pentane, hexanes, heptanes, petroleum distillates or other liquids providing a suitable boiling point range of the propellant, preferably all up to 50% by weight. In particular, preferred hydrocarbons for use in combination with isooctane are isobutane, isopentane, n-pentane, n-hexane, petroleum ether and n-heptane.

Suitably, the propellant is a liquid at room temperature and has a boiling point below the softening point of the polymer shell at atmospheric pressure. Preferably, the propellant comprises about 10% to about 30%, most preferably about 15% to about 25% by weight of the total microspheres.

Apart from the polymer shell and the propellant, the microspheres may comprise another material, which is usually added in an amount of about 1 to about 20 weight percent, preferably about 2 to about 10 weight percent, during the manufacture of the microspheres. Examples of such materials are solids such as one or more silica, chalk, bentonite, starch, crosslinked polymers, methyl cellulose, gum agar, hydroxypropyl methylcellulose, carboxy methylcellulose, colloidal clays Solid suspending agents and / or one or more salts, oxides or hydroxides of metals such as Al, Ca, Mg, Ba, Fe, Zn, Ni and Mn, for example one or more calcium phosphates, carbonic acid Calcium, magnesium hydroxide, barium sulfate, calcium oxalate and hydroxides of aluminum, iron, zinc, nickel or manganese. If present, these solid suspending agents are usually located primarily on the outer surface of the polymer shell. However, although the suspending agent was added during the preparation of the microspheres, the suspending agent was washed in a later step and thus may not actually be present in the final product.

Preferably, the microspheres of the composition have a relatively high T _start and T _max . T _start is preferably in the range of about 80 to about 200 ° C., more preferably about 130 to about 190 ° C., most preferably about 150 to about 180 ° C., while T _max is preferably less than about 190 ° C. High, most preferably higher than about 200 ° C. Usually T _max does not exceed about 300 ° C.

The average particle size of the expandable microspheres is suitably about 1 to about 500 μm, preferably about 3 to about 200 μm, most preferably about 5 to about 100 μm. By heating to a temperature above T _start , it is usually possible to expand the microspheres to a diameter of about 2 to about 7 times, preferably about 4 to 7 times.

Expandable microspheres as described above are commercially available under the trademark Expancel® DU and are described, for example, in previously mentioned US Pat. Nos. US 3615972, US 3945956, US 5536756, US 6235800, Can be produced by methods known in the art, as disclosed in US Pat. Nos. 6235394 and US 6509384, European Patent EP 486080, Japanese Patent Application Publication No. 87-286534, and International Publication WO2004 / 072160. have. Expanded microspheres are also commercially available, for example under the trademark Expancel® DE.

The at least one inhibitor in the composition of the invention is preferably a substance which decomposes or otherwise reacts to form at least one acid under prevailing conditions during processing of the acid or their precursor, ie the polymer resin. Such precursors include, for example, anhydrides of acids. The acid may also be a hydrated form of the acid. The melting point of the acid or acid hydrate is less than about 200 ° C, preferably less than about 150 ° C. There is no critical lower limit and the inhibitor may have a melting point of at least about 0 ° C. or at least about 30 ° C., for example.

The acid is preferably an organic acid, preferably an organic acid containing at least one carboxyl group in the solid form of the acid.

Groups of acids useful as inhibitors include their precursors, such as formic acid, benzoic acid, oxalic acid, azelaic acid, malonic acid, malic acid, succinic acid, maleic acid, phthalic acid, acrylic acid, methacrylic acid, mixtures thereof and anhydrides. Particularly preferred inhibitors include azelaic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, oxalic acid, succinic acid, succinic anhydride and mixtures thereof.

In an embodiment of the present invention, the composition is a mixture of two or more inhibitors as described above, or another compound, such as citric acid, their precursors or other compounds useful as chemical blowing agents and one as described above. Combinations of inhibitors. Useful combinations include maleic acid or precursors thereof, such as maleic anhydride and one or more oxalic acid or azelaic acid or precursors thereof. In addition, the at least one inhibitor may also be, for example, a mixture comprising maleic acid and citric acid or one or more precursors to at least one of maleic acid and citric acid.

The amount of inhibitor in the composition is preferably from about 0.1 to about 20 weight percent, most preferably from about 0.5 to about 15 weight percent, particularly most preferably from about 1 to about 10 weight percent, based on the expandable microspheres. .

The compositions of the present invention can be prepared by any realistic method, for example by dry mixing expanded or expandable microspheres with an inhibitor, or by mixing microspheres with a solution of the inhibitor. It is also possible to mix the microspheres with the salts of the inhibitor and acidify the salts in order to obtain the acid in a later step. If the microspheres contain alkaline substances, such as hydroxides of metals, on their surfaces, in some cases it may be appropriate to remove these substances completely or partially before mixing with the inhibitor.

A composition comprising the aforementioned expanded or expandable microspheres and at least one inhibitor can be used in the processing of various types of polymeric thermoplastic and thermosetting resins, for example by mixing the composition with a polymer resin to form a polymer resin, expandable microspheres. And at least one inhibitor. However, such compositions comprising a polymeric resin can also be prepared by separately adding the components, where the preferred relative amounts of microspheres and inhibitors are as described above.

Examples of polymeric resins include polyolefins, TPEs (thermoplastic elastomers), thermoplastic polyesters, polycarbonates, polyamides, acetals, styrenic polymers and PVC and copolymers thereof. Examples of polyolefins include polypropenes, polyethenes and copolymers thereof. Examples of thermoplastic elastomers include styrene block copolymers such as styrene butadiene styrene (SBS) and styrene ethylene butadiene styrene (SEBS), olefinic thermoplastic / rubber mixtures such as thermoplastic polyolefin (TPO) and TPE-O (thermoplastic elastomer olefinic), Thermoplastic polyurethane block copolymers, TPU (thermoplastic urethane) and TPE-U (thermoplastic elastomer urethane), thermoplastic ether / ester copolymers such as TEEE (thermoplastic elastomer ether ester block copolymer), and TPE-A (thermoplastic elastomer amide) And copolyamides such as COPA (copolyamide). Examples of thermoplastic polyesters include PET (polyethylene terephthalate) and PBT (polybutadiene terephthalate). Examples of polyamides include PA 6, PA 66, PA 11 and PA 12. Examples of acetals include POM (polyoxymethylene). Examples of styrene-based polymers include PS (polystyrene), ABS (acrylonitrile butadiene styrene) and SAN (styrene acrylonitrile).

It has been found that the present invention is beneficial for processing high melting point polymer resins, for example at least 100 ° C or at least 180 ° C. Such polymer resins contain at least 50 mole percent, most preferably at least 80 mole percent of monomers of any propylene, styrene or ethylene, polypropylene, polystyrene, HD polyethylene and copolymers thereof.

When processing polymer resin compositions comprising expanded or expandable microspheres and at least one inhibitor, conventional methods and apparatus may be used alone or in combination, for example one or more calendering. , Extrusion, blow and injection molding. The processing is carried out at elevated temperatures, preferably at least at about 100 ° C., most preferably at least at about 180 ° C., for example at about 180 to about 300 ° C. or at about 210 to about 250 ° C. If expandable microspheres are used, the microspheres will cause foaming of the polymer resin during processing.

Expanded or expandable microspheres and at least one inhibitor, as described above, can be added to and mixed with the resin at any time as a pre-manufactured composition as described above or separately. For example, the microspheres and inhibitors can be added and mixed directly into the powder or granules of the resin before or after being filled into the device. If mixed before being filled into the device, the components may be optionally not expanded without inflating the microspheres, such as, for example, extruding optionally with another desired additive during final processing at a temperature below the prevailing pressure and expansion temperature. It is possible to provide compounds or simple mixtures which are prepared by the method of granulating together.

The amount of polymeric resin in the composition is preferably about 70 to about 99.5 weight percent, most preferably about 80 to about 90 weight percent. The amount of expandable microspheres is preferably about 0.5 to about 20 weight percent, most preferably about 1 to about 10 weight percent. The amount of inhibitor is preferably as described above.

Low melt polyolefins, for example EVA (ethyl-vinyl acetate), EBA (ethyl-butyl acrylate), EMA (ethyl-methyl acrylate), ethylene-octene copolymer or low melting polyethylene; It is also possible to add microspheres contained in a masterbatch of a resin having a low melting point, such as a copolymer of. The masterbatch may also include an inhibitor as described above, otherwise the inhibitor is preferably added to the resin separately. When a masterbatch is used, the content of microspheres therein is preferably about 10 to about 90% by weight, most preferably about 20 to about 75% by weight.

When operating the apparatus, heat is treated to obtain a temperature sufficient to melt the resin, for example at least about 100 ° C or at least about 180 ° C. The actual molding or calendering then takes place, ie the molten resin is forced through a continuous calender roller or extrusion die or injected into a mold by any suitable means such as a molding screw. do. In calendering using inflatable microspheres, most of the expansion takes place between rollers, while in extrusion or molding using inflatable microspheres, although the temperature is significantly lower, the pressure is lost after passing through the die or in the mold. When released, expansion occurs mainly. Thus, most of the expansion of the microspheres occurs after passing the forming screw, or else fully expanded microspheres may have been destroyed by strong shear forces.

The process of the present invention has been found to be particularly beneficial for the production of lightweight objects that have passed through injection molding. The high quality object is from polypropylene and other high melting polymers and / or at elevated temperatures, optionally in a molten state, for a long time, for example from about 3 minutes to about 5 hours or from about 5 minutes to It has also been found that for about 2 hours it can be obtained when held. Expanded microspheres that do not cause significant foaming on their own are particularly beneficial for thermosetting resins with short cure times such as polyurethane, phenol or epoxy resins.

The invention will be further described with reference to the following examples which are not to be considered as limiting its scope. Unless stated otherwise, all parts and ratios refer to weight percent and parts by weight.

Example 1.

Expandable MS (microspheres) of type Expancel® 980 DU 120 were dry-mixed with different amounts of inhibitor. 2% by weight of this mixture was then mixed with PP (polypropene) beads from Borealis (BF330 MO MFR 18 g / 10 min 230 ° C., 2.16 kg). The mixture of PP, MS and stabilizer was molded in a Demag Ergotech injection molding apparatus with a 50 ton clamping force and a 40 mm screw to form a 5 mm thick 100 × 50 mm plate. The injection rate was 140 ccm / sec, the set temperature from the hopper to the nose was 190-200-220-230 ° C., the mold temperature was 15 ° C., and the cooling time was 90 sec. The brightness of the molded PP plate was measured using Minolta Spectrophotometer CM 3610 d. The results are shown in the table below:

Inhibitor Weight percent of inhibitor in MS magnitude(%) Remark Not added (control) 0 15 Oxalic Acid Di-hydrate 5 36 Improved Molding Fill Azela Mountain 5 30 Improved Molding Fill Sodium formaldehyde sulfoxylate 5 23 Oxalic Acid Di-hydrate 0.5 24

Example 2.

A mixture of Expancel 980 DU 120 and 5 wt% inhibitor was tested as in Example 1. The results are shown in the table below:

Inhibitor Weight percent of inhibitor in MS magnitude(%) Remark Not added (control) 0 16 Not added (control) 0 14 Maleic acid + citric acid mono-hydrate 3 + 2 55 Improved Molding Fill

Example 3.

A mixture of Expancel 980 DU 120 and 5 wt.% Of inhibitor was tested as in Example 1 except that the set temperature from hopper to nose was 190-200-210-230 ° C. The results are shown in the table below:

Inhibitor Weight percent of inhibitor in MS magnitude(%) Remark Not added (control) 0 21 Benzoic acid 5 32 Maleic anhydride 5 56 Maleic acid 5 62 Not added (control) 0 22

Example 4.

A mixture of Expancel 980 DU 120 and 1 wt% inhibitor was tested as in Example 3 except that the cooling time was 60 sec. The results are shown in the table below:

Inhibitor Weight percent of inhibitor in MS magnitude(%) Remark Not added (control) 0 34 Maleic acid One 56 Malonic acid One 48 Acrylic acid One 43 Succinic acid One 52 Not added (control) 0 32 Maleic acid One 55 Phthalic anhydride One 54

Example 5.

A mixture of Expancel 980 DU 120 and various amounts of inhibitor was tested as in Example 1 except that the set temperature from hopper to nose was 190-200-210-230 ° C. The results are shown in the table below:

Inhibitor Weight percent of inhibitor in MS magnitude(%) Remark Not added (control) 0 26 Maleic acid 0.5 40 Maleic acid One 49 Maleic acid 2 57 Maleic acid 3 61 Maleic acid 4 62 Maleic acid 5 62 Citric Acid Mono-hydrate One 41 Citric Acid Mono-hydrate 3 47 Improved Molding Fill Citric Acid Mono-hydrate 5 46 Improved Molding Fill

The examples show that the inclusion of the inhibitor according to the invention improves the brightness of the shaped object and in some cases also improves the molding-filling. However, although the results in each test have been found to be reproducible, the absolute value of luminosity in other embodiments (ie other tests) is completely comparable due to different temperature aspects and / or different cooling times in the device. Note that it is not worth it.

The present invention provides a thermally unexpanded thermal system comprising about 0.1 to about 50 weight percent of at least one inhibitor selected from the group consisting of acids having melting points below 200 ° C. and precursors thereof, and a thermoplastic polymer shell encapsulating the propellant. It relates to a solid powder composition comprising microspheres that are expandable. The present invention further relates to the manufacture and use thereof, to compositions comprising the polymer resin, to the preparation thereof, to processes for processing the polymer resin, and to the materials obtainable thereby.

Claims (19)

Expanded or unexpanded thermally expandable microspheres comprising a thermoplastic polymer shell encapsulating the propellant; And 0.1 to 50% by weight of at least one inhibitor; The propellant is a liquid having a boiling point not higher than the softening temperature of the thermoplastic polymer shell, The thermoplastic polymer shell is produced from a mono- or co-polymer obtained by polymerizing ethylenically unsaturated monomers, The inhibitor is at least one selected from the group consisting of formic acid, benzoic acid, oxalic acid, azelaic acid, malonic acid, malic acid, succinic acid, maleic acid, phthalic acid, acrylic acid, methacrylic acid and precursors thereof Solid powder composition, characterized in that. 70 to 99.5 weight percent polymer resin; Expanded or unexpanded thermally expandable microspheres comprising a thermoplastic polymer shell encapsulating the propellant; And from 0.1 to 50% by weight of at least one inhibitor based on the amount of microspheres, The polymer resin includes at least one of polyolefin, TPE (thermoplastic elastomer), thermoplastic polyester, polycarbonate, polyamide, acetal, styrenic polymer and PVC and copolymers thereof, The propellant is a liquid having a boiling point not higher than the softening temperature of the thermoplastic polymer shell, The thermoplastic polymer shell is produced from a mono- or co-polymer obtained by polymerizing ethylenically unsaturated monomers, The inhibitor is at least one selected from the group consisting of formic acid, benzoic acid, oxalic acid, azelaic acid, malonic acid, malic acid, succinic acid, maleic acid, phthalic acid, acrylic acid, methacrylic acid and precursors thereof Composition characterized in that. The composition of claim 1 or 2, wherein the composition comprises thermally expandable microspheres that are not expanded. The composition of claim 1 or 2 comprising expanded microspheres. delete The composition of claim 1 or 2, wherein the ethylenically unsaturated monomer comprises a nitrile containing monomer. delete delete The composition of claim 1 or 2, wherein the at least one inhibitor is selected from the group consisting of maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, oxalic acid, succinic acid, succinic anhydride and mixtures thereof. 10. The composition of claim 9, wherein the at least one inhibitor comprises maleic acid or maleic anhydride. The composition of claim 2 wherein the composition comprising the polymer resin comprises 0.5 to 20 weight percent microspheres. A method of making a composition according to claim 1 comprising mixing expanded or unexpanded thermally expandable microspheres comprising a thermoplastic polymer shell encapsulating a propellant with 0.1 to 50% by weight of at least one inhibitor. To The propellant is a liquid having a boiling point not higher than the softening temperature of the thermoplastic polymer shell, The thermoplastic polymer shell is produced from a mono- or co-polymer obtained by polymerizing ethylenically unsaturated monomers, The inhibitor is at least one selected from the group consisting of formic acid, benzoic acid, oxalic acid, azelaic acid, malonic acid, malic acid, succinic acid, maleic acid, phthalic acid, acrylic acid, methacrylic acid and precursors thereof Method for producing a composition, characterized in that. 70 to 99.5 weight percent polymer resin; Expanded or unexpanded thermally expandable microspheres comprising a thermoplastic polymer shell encapsulating the propellant; And from 0.1 to 50% by weight of at least one inhibitor based on the amount of microspheres. The polymer resin includes at least one of polyolefin, TPE (thermoplastic elastomer), thermoplastic polyester, polycarbonate, polyamide, acetal, styrenic polymer and PVC and copolymers thereof, The propellant is a liquid having a boiling point not higher than the softening temperature of the thermoplastic polymer shell, The thermoplastic polymer shell is produced from a mono- or co-polymer obtained by polymerizing ethylenically unsaturated monomers, The inhibitor is at least one selected from the group consisting of formic acid, benzoic acid, oxalic acid, azelaic acid, malonic acid, malic acid, succinic acid, maleic acid, phthalic acid, acrylic acid, methacrylic acid and precursors thereof Method for producing a composition, characterized in that. A first method characterized in that it is used as an additive in the processing of polymer resins comprising at least one of polyolefins, TPEs (thermoplastic elastomers), thermoplastic polyesters, polycarbonates, polyamides, acetals, styrenic polymers and PVC and copolymers thereof. A composition according to claim.  In a method for processing a polymer resin in a composition according to claim 2, the polymer resin is a polyolefin, TPE (thermoplastic elastomer), thermoplastic polyester, polycarbonate, polyamide, acetal, styrene-based polymers and PVC and copolymers thereof And at least one of: heating the resin and shaping the resin into the desired shape. The method of claim 15, wherein the processing is performed at a temperature of at least 100 ° C. 16. 17. The method of claim 16, wherein the processing is performed at a temperature of at least 180 ° C. 18. The method of any one of claims 15 to 17, wherein the processing comprises one or more calendering, extrusion, blow and injection molding. The polymer material according to any one of claims 15 to 17, comprising at least one of polyolefin, TPE (thermoplastic elastomer), thermoplastic polyester, polycarbonate, polyamide, acetal, styrenic polymer and PVC and copolymers thereof. Product obtainable by a process according to the invention.