GB2489123A - Encapsulated tin (II) chloride - Google Patents

Encapsulated tin (II) chloride Download PDF

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Publication number
GB2489123A
GB2489123A GB1208928.0A GB201208928A GB2489123A GB 2489123 A GB2489123 A GB 2489123A GB 201208928 A GB201208928 A GB 201208928A GB 2489123 A GB2489123 A GB 2489123A
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GB
United Kingdom
Prior art keywords
chloride
tin
thermoplastic polymer
composition
weight
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Granted
Application number
GB1208928.0A
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GB201208928D0 (en
GB2489123B (en
Inventor
John Williams
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William Blythe Ltd
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William Blythe Ltd
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Priority to GB1208928.0A priority Critical patent/GB2489123B/en
Priority claimed from GB0725188.7A external-priority patent/GB2455981B/en
Publication of GB201208928D0 publication Critical patent/GB201208928D0/en
Publication of GB2489123A publication Critical patent/GB2489123A/en
Application granted granted Critical
Publication of GB2489123B publication Critical patent/GB2489123B/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/04—Halides
    • C01G19/06—Stannous chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Abstract

The invention provides a composition comprising 1-60 weight % tin (II) chloride dihydrate, encapsulated by a thermoplastic polymer (polypropylene or polyethylene) having melting point greater than 40 degrees C, wherein the composition is extruded at less than 150 degrees C and under sufficient pressure to prevent steam formation before cooling. The composition provides low abrasion on encapsulation and high activity on cooling.

Description

Encapsulated Tin(II)Chloride The present invention concerns encapsulated tin(II) chloride (SnC12) compositions. Tn particular, the present invention concems a composition comprising tin(IT) chloride encapsulated by a polymer, methods of preparation thereof and uses therefor.
Tin (II) chloride is hygroscopic and can oxidise over time to a tin (TV) salt. The low melting point of tin(II) chloride dihydrate, of 39°C also means that transportation of the material can be problematic, as initially free flowing powder, crystal or flake can agglomerate on transport due to exposure to temperatures of 39°C or above, resuhing in material that is no longer readily handled or dissolved. A combination of low melting point and hygroscopicity results in frequent handling problems and inaccurate dosing such as from the forming of aggregates i.e. caking. There is therefore a need to improve handling, storage and transport characteristics of tin (TI) chloride.
Further, even when tin(IT) chloride anhydrous is used, mehing point 247°C, the hygroscopicity of the material provides similar handling problems due to adsorption N of water and consequent caking effects.
LI) Tin (II) chloride, also known as stannous chloride, is classified as an irritant' and can be the most hazardous material used in some production processes, such as in plastics manufacturing, such in reactive injection moulding or tin plating, such as of circuit boards. There is therefore a need to improve safety of handling.
Tin (II) chloride, is used in the plastics industry as a catalyst. However, the above problems prevent its efficient usage, and the low levels of its use and different handling characteristics mean that it cannot be handled as conveniently as, for example, would a pigment master batch.
It is an object of the present invention to obviate or mitigate the above disadvantages and provide tin (II) chloride in a product form that has at least one of the characteristics of, lower caking and agglomeration, safer handling and bulked amount for easier dosage in plastics manufacture, such as manufacture of plastics articles by extrusion.
Another object of the present invention is to provide a process for producing said product form, such as in pellet form, comprising tin (II), preferably tin(H) chloride..
The present invention in its various aspects is as set out in the accompanying claims.
A composition comprising tin (II) chloride, encapsulated by a thermoplastic polymer.
The tin (II) chloride may have the formula SnC12.xH2O, wherein x is from 0 to 2. The tin (II) chloride used in the invention is preferably anhydrous hydrated tin(II) chloride of formula SnCl2.xH2O, wherein x is 0, so as to prevent gassing of steam in an extrusion process.
In the present invention the term thermoplastic polymer means a polymer that becomes reversibly plastic upon heating. The term thermoplastic polymer, whilst preferably being a single polymer, either copolymer or homopolymer, may comprise CJ one or more polymers. A homopolymer is preferred. r
N The polymer may be a water insoluble polymer. Preferred water insoluble polymers are ethyl vinyl acetate (EVA) polyethylene and polypropylene as they are particularly If) hydrophobic. The composition of the present invention may consist of polypropylene and tin (II) chloride. The polypropylene may comprise crystalline polypropylene.
In another embodiment, the polymer may be a water soluble polymer. Water soluble polymers include hydroxy and carboxy functionalised polymers. Preferred water insoluble polymers are poly methacrylic and poly acrylic acid based polymers. Such polymers may comprise comonomers, such as esters provided that the polymer remains water soluble. Soluble polymers provide a convenient delivery vehicle to provide tin (II) chloride solutions.
In the present invention water soluble means having a solubility in water of greater than 10% by weight at 20°C.
In the present invention encapsulation means that material, the encapsulated material, here tin(II) chloride is surrounded by an encapsulate, here a thermoplastic polymer.
An encapsulated material may typically comprise small amounts of material (<10% preferably <1%) which are not encapsulated incidental to the encapsulated material.
The composition of the present invention, may have tin(II) chloride present in an amount from 0.1 to 60 by weight %, and the thermoplastic polymer is present in an amount from 99.9 to 40% by weight. Preferably, the tin(II) chloride is present in an amount from 10 to 50 by weight %, and the thermoplastic polymer present in an amount from 90 to 50% by weight. Most preferably, the tin(II) chloride is present in an amount from 15 to 35 by weight %, and the thermoplastic polymer is present in an amount from 85 to 65 % by weight. Most preferably, the tin(II) chloride is present in an amount of 20 % by weight, and the thermoplastic polymer, preferably polypropylene, is present in an amount of 80 % by weight. Not only can the above compositions provide a free flowing, non-hygroscopic and non-toxic form of tin (TI) chloride but the bulking up of the material by the encapsulate enables more accurate dosing of material as a greater weight is added to provide a given activity oftin salt. c\J
In another aspect of the present invention there is provided a process for producing Ft the composition of tin (TI) chloride encapsulated in a thermoplastic polymer, the process comprising the steps of LI) (i) providing the polymer in the form of a thermoplastic polymer and also providing particulate tin (II) chloride; (ii) providing an extruder, the temperature within said extruder (a) increasing along the length of said extruder, and (b) being sufficient, in combination with the forces exerted within, to melt the thermoplastic polymer; (iii) feeding a mixture of the particulate tin (II) chloride and the thermoplastic polymer into said extruder; (iv) feeding the mixture of particulate tin (II) chloride and at thermoplastic polymer along the length of said extruder such that said thermoplastic polymer melts, and said tin (II) chloride becomes dispersed within said thermoplastic polymer; (v) extruding the molten thermoplastic polymer / tin (II) chloride mixture through a die, wherein cooling of said extruded mixture results in setting of said thermoplastic polymer, encapsulating said tin (II) chloride; and (vi) chopping the extruded thermoplastic polymer encapsulated tin (TI) chloride to form pellets.
In the present invention, particulate tin (II) chloride is preferably in the form of crystals having no occluded or entrained air or water. The particulate tin(II) chloride is preferably anhydrous tin(II)chloride. The particle size of the particulate tin (II) chloride is preferably between 10 and 2,000 jim, more preferably between 50 and 1,000 jim. If a flake is used then a size range of 2mm to 10mm is preferred as it is less prone to agglomeration in charging the extruder and on storage and has lower hygroscopicity.
If tin (II) chloride dihydrate is used, the melting point of the thermoplastic is preferably greater than 40°C so as to melt the tin (II) chloride during encapsulation.
C\j Strictly speaking the tin (II) chloride dissolves in its own water if crystallisation, having the appearance of melting. This reduces abrasion of the extruder and improves Ft tin (II) chloride distribution in the polymer but requires a corrosion resistant extruder components. If tin (II) chloride dihydrate is used, the melting point of the If) thermoplastic is preferably less than 150°C, more preferably less than 100°C sO as to prevent the formation of steam in the extruded material. However, extrusion with cooling under pressure, such as in to a mould may utilise temperatures above 100°C during encapsulation provided sufficient pressure is present to prevent steam formation. In this respect tin (II) chloride monohydrate is preferred as this does not give rise to steam except at high temperature and reduced pressure.
Further, melting may preferably provide elongate particles of tin (II) chloride from the dihydrate, on cooling, so as to provide a high surface area of polymer for reaction or dissolution. This also enables relatively coarse tin (II) chloride to be used, such as flake, so that dusting and water absorbtion of the tin (II) chloride in steps (i) to (iii) of the process is minimised.
The properties defined for the tin (II) chloride and the thermoplastic polymer and of the composition as provided herein apply to the composition of the invention, to the method of production and to uses of the present invention.
The composition of the invention, such as produced by the process of the present invention, may be used, for example, in the production of an elastomeric material for the purposes of crosslinking a polymer mixture comprising natural rubber by means of extrusion the polymer mixture with the composition at a temperature above the melting point of the encapsulating thermoplastic polymer. The thermoplastic polymer is preferably polypropylene. The polymer mixture preferably comprises linked natural rubber and polypropylene. The composition of the invention may be mixed with kaolin and chopped rubber in a premix hoper before co-extrusion with polypropylene.
The encapsulate of the present invention, in the form of tin (IT) chloride encapsulated in a soluble polymer, preferably a methacrylic or acrylic acid based polymer may be used as a source of tin (IT) for use as a reducing agent in organic synthesis. The encapsulating polymer is preferably soluble in water or a polar aprotic solvent, such N as acetone. The use provides a convenient anhydrous method of removing the polymer coating, such as may be carried out in anhydrous conditions, optionally under LI) an inert gas, such as nitrogen, to provide pure tin (II) chloride free form oxidation and suitable for the synthesis of fine chemicals, such as pharmaceuticals. The tin (II) chloride may be anhydrous. The polymer is preferably a polymer soluble in water or, to the same level, in an anhydrous polar aprotic solvent.
The encapsulate of the present invention, in the form of tin (II) chloride coated encapsulated in a water soluble polymer, preferably a methacrylic or acrylic acid based polymer may be used as a source of tin (II) for tin plating printed wiring boards.
The polymer is preferably a polymer active in tin plating such a polymer used as a levelling or brightening agent.
In the present invention tin(II)chloride may be replaced in the composition and production process by one or more of Arsenic Acid, Copper Carbonate, Copper Oxide, Copper Pyrophosphatc, Cupric Bromide, Cupric Chloride Anhydrous, Cupric Chloride Dihydrate, Cuprous Bromide, Cuprous Iodide, Potassium Todate, Potassium Stannate, Sodium Arsenite, Sodium Iodide, Sodium Stannate, Stannous Oxalate, Stannous Oxide, Stannous Sulphate, Zinc Chloride and Zinc Sulphate.
A masterbatch is a concentrated mixture of pigments and/or additives, encapsulated during a heat process into a carrier resin which is then cooled and cut into a granular shape. Masterbatch allows the processor to colour raw polymer or add components economically during the plastics manufacturing process. The present invention encompasses masterbatch comprising polymer and one or more of the inorganic salts disclosed herein as hereinbefore disclosed. c\J r
LU c\J

Claims (10)

  1. Claims 1. A composition consisting of from 1 to 60 by weight % of stannous chloride dihydrate by weight and the remainder to 100% by weight consisting of polypropylene or polyethylene having a melting point of greater than 40° C, wherein the composition is extruded at less than 150°C and under sufficient pressure to prevent steam formation before cooling.
  2. 2. The composition of claim 1 wherein extrusion takes place at less than 100°C.
  3. 3. A process for producing the composition according to any preceding claim, the process comprising the steps of (i) polypropylene or polyethylene having a melting point of greater than 40°C (ii) providing particulate tin(TI)chloride dihydrate (iii) providing an extruder, the temperature within said extruder (a) increasing along the length of said extruder, and (b) being sufficient, in combination with the pressure exerted within, to melt the thermoplastic polymer; (iv) feeding a mixture of the particulate tin(II) chloride and the thermoplastic polymer into said extruder; being 1 to 60 by weight % of stannous chloride dihydrate by weight and the remainder to 100% by weight comprising polypropylene or polyethylene (v) feeding the mixture of particulate tin(1I) chloride and at least one thermoplastic polymer along the length of said extruder such that said thermoplastic polymer mehs at 150°C or below, and said tin(II) chloride becomes dispersed within said at least one thermoplastic polymer; (vi) extruding the molten at least one thermoplastic polymer / tin(11) chloride mixture through a die, wherein cooling of said extruded mixture results in setting of said thermoplastic polymer, encapsulating said tin(II) chloride; and chopping the extruded thermoplastic polymer encapsulated tin(IT) chloride to form pellets.
  4. 4. The composition of claim 1 wherein extrusion takes place at less than 100°C.Amendments to the claims have been made as follows: Claims, 8 1. A composition consisting of from 1 to 60 by weight % of stannous chloride dihydrate by weight and the remainder to 100% by weight consisting of polypropylene or polyethylene or a mixture thereof having a melting point of greater than 40°C, wherein the composition is extruded at less than 150°C and under sufficient pressure to prevent steam formation before cooling.2. The composition of claim 1 wherein extrusion takes place at less than 100°C.3. The composition of claim 1 or claim 2 wherein the composition consists of polypropylene and stannous chloride dihydrate.4. The composition of claim 1, 2 or 3 wherein the particle size of the particulate tin (II) chloride is between 10 and 2,000pm c\J
  5. 5. A process for producing the composition according to any preceding claim, the Ft process comprising the steps of (i) providing polypropylene or polyethylene or a mixture thereof C") having a melting point of greater than 40°C (ii) providing particulate tin(II)chloride dihydrate (iii) providing an extruder, the temperature within said extruder (a) increasing along the length of said extruder, and (b) being sufficient, in combination with the pressure exerted within, to melt the thermoplastic polymer; (iv) feeding a mixture of the particulate tin(II) chloride and the thermoplastic polymer into said extruder; being 1 to 60 by weight % of stannous chloride dihydrate by weight and the remainder to 100% by weight comprising polypropylene or polyethylene (v) feeding the mixture of particulate tin(II) chloride and at least one thermoplastic polymer along the length of said extruder such that said thermoplastic polymer melts at 150°C or below, and said tin(II) chloride becomes dispersed within said at least one thermoplastic polymer; (vi) extruding the molten at least one thermoplastic polymer / tin(II) chloride mixture through a die, wherein cooling of said extruded mixture results in sefting of said thermoplastic polymer, encapsulating said tin(II) chloride; and chopping the extruded thermoplastic polymer encapsulated tin(II) chloride to form pellets.
  6. 6. The process of claim 5 wherein extrusion takes place at less than 100°C.
  7. 7. The process of claim 5 or claim 6 wherein the composition consists of polypropylene and stannous chloride dihydrate.
  8. 8. The process of claim 5, 6 or 7 wherein the particle size of the particulate tin (II) chloride is between 10 and 2,000pm.
  9. 9. The process of any of claims S to 8 wherein the particulate tin(II)chloride dehydrate is provided in the form of a flake in a size range of 2mm to 10mm. rN
  10. 10. Use of the composition of any of claims 1 to 4, or the composition as produced in any of claims S to 9, in the production of an elastomeric material for the purposes of CO crossliiiking a polymer mixture comprising natural rubber by means of extrusion the polymer mixture with the composition at a temperature above the mehing point of the encapsulating polypropylene or polyethylene.
GB1208928.0A 2007-12-22 2007-12-22 Encapsulated tin (II) chloride dihydrate Active GB2489123B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1208928.0A GB2489123B (en) 2007-12-22 2007-12-22 Encapsulated tin (II) chloride dihydrate
GB0725188.7A GB2455981B (en) 2007-12-22 2007-12-22 Encapsulated Anhydrous Tin (II) chloride

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GB201208928D0 GB201208928D0 (en) 2012-07-04
GB2489123A true GB2489123A (en) 2012-09-19
GB2489123B GB2489123B (en) 2012-10-31

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2516235A (en) * 2013-07-15 2015-01-21 William Blythe Ltd Free flowing stannous chloride
WO2015008053A1 (en) * 2013-07-15 2015-01-22 William Blythe Limited Free flowing stannous chloride in thermoplastic carrier
US10047226B2 (en) 2015-05-22 2018-08-14 William Blythe Limited Provision of inorganic powders with reduced hazard
CN110563029A (en) * 2019-10-30 2019-12-13 广东先导稀材股份有限公司 Stannous chloride dihydrate and preparation method thereof
US10730206B2 (en) 2015-02-26 2020-08-04 Exxonmobil Chemical Patents Inc. Process for forming thermoplastic vulcanizates and thermoplastic vulcanizates made therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU427034A1 (en) * 1971-09-21 1974-05-05 Воронежский технологический институт
JPS6213457A (en) * 1985-07-10 1987-01-22 Kohjin Co Ltd Production of thermoplastic resin composition
WO2005028556A1 (en) * 2003-09-17 2005-03-31 Advanced Elastomer Systems Thermoplastic vulcanizates and process for making the same
WO2007073479A2 (en) * 2005-12-20 2007-06-28 Curative Technologies Corporation Radiotherapeutic high specific activity tin-117m and methods of use
DE102006002759A1 (en) * 2006-01-20 2007-07-26 Rehau Ag + Co. Thermoplastic elastomer for extrusion or injection molding e.g. to seal, profile or shock absorber contains ethylene-propylene-diene monomer terpolymer, polypropylene and polystyrene-b-(poly(ethylene/ethylene/propylene)-b-polystyrene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU427034A1 (en) * 1971-09-21 1974-05-05 Воронежский технологический институт
JPS6213457A (en) * 1985-07-10 1987-01-22 Kohjin Co Ltd Production of thermoplastic resin composition
WO2005028556A1 (en) * 2003-09-17 2005-03-31 Advanced Elastomer Systems Thermoplastic vulcanizates and process for making the same
WO2007073479A2 (en) * 2005-12-20 2007-06-28 Curative Technologies Corporation Radiotherapeutic high specific activity tin-117m and methods of use
DE102006002759A1 (en) * 2006-01-20 2007-07-26 Rehau Ag + Co. Thermoplastic elastomer for extrusion or injection molding e.g. to seal, profile or shock absorber contains ethylene-propylene-diene monomer terpolymer, polypropylene and polystyrene-b-(poly(ethylene/ethylene/propylene)-b-polystyrene

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2516235A (en) * 2013-07-15 2015-01-21 William Blythe Ltd Free flowing stannous chloride
WO2015008053A1 (en) * 2013-07-15 2015-01-22 William Blythe Limited Free flowing stannous chloride in thermoplastic carrier
GB2516235B (en) * 2013-07-15 2015-12-30 William Blythe Ltd Free flowing stannous chloride
US10730206B2 (en) 2015-02-26 2020-08-04 Exxonmobil Chemical Patents Inc. Process for forming thermoplastic vulcanizates and thermoplastic vulcanizates made therefrom
US10047226B2 (en) 2015-05-22 2018-08-14 William Blythe Limited Provision of inorganic powders with reduced hazard
CN110563029A (en) * 2019-10-30 2019-12-13 广东先导稀材股份有限公司 Stannous chloride dihydrate and preparation method thereof

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GB201208928D0 (en) 2012-07-04
GB2489123B (en) 2012-10-31

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