WO2013117488A1 - Co-polymers containing silicone - Google Patents

Abstract

The invention provides a process for forming a co-polymer containing silicone comprising; a) dispersing an emulsion comprising water, a silicone compound and a ethylene oxide/propylene oxide block copolymer, with at least one monomer able to form condensation polymer by poly-condensation reaction and b) reacting the silicone compound with the monomer to form a co-polymer containing silicone units. This permits to incorporate silicone into condensation-type polymers to improve their properties.

Description

CO-POLYMERS CONTAINING SILICONE

BACKGROUND OF THE INVENTION

[0001] WO2012002571 describes an oil-in-water silicone emulsion having a low silicone oligomer content, and capable of forming a cured film exhibiting sufficient strength and sufficient adhesion to a substrate by the removal of water content even without using an organotin compound as a curing catalyst. The oil-in-water silicone emulsion composition comprises: (A) 100 parts by mass of a polyorganosiloxane having at least two groups per molecule selected from a group comprising a hydroxyl group bonded to a silicon atom, an alkoxy group, and an alkoxyalkoxy group; (B) 0.1 -200 parts by mass of colloidal silica; (C) 0.1 -100 parts by mass of an aminoxy group-containing organosilicon compound having on average two aminoxy groups bonded to silicon atoms per molecule; (D) 1 -100 parts by mass of an ionic emulsifier; (E) 0.1 -50 parts by mass of a non-ionic emulsifier; and (F) 10- 500 parts by mass of water. The nonionic emulsifier is polyoxyethylene polyoxypropylene copolymerization component-shaped nonionic emulsifier of formula:

HO(CH2CH20)a(CH(CH3)CH20)b(CH2CH20)cH (I) or

HO(CH(CH3)CH20)d(CH2CH20)e(CH(CH3)CH20)fH (I I ).a-f= 1 -350.

[0002] WO2010104186 describes an oil-in-water silicone emulsion composition comprising (A) 100 mass parts of a polyorganosiloxane that contains in each molecule at least two silicon-bonded hydroxyl or hydrolyzable groups, (B) 0.1 to 200 mass parts of a colloidal silica, (C) 1 to 100 mass parts of an ionic emulsifying agent, (D) 0.1 to 50 mass parts of a polyoxyethylene-polyoxypropylene copolymer-type nonionic emulsifying agent, and (E) 10 to 200 mass parts water.

[0003] US201 10245374 describes a water-oil-water (w/o/w) multiple emulsion (E1 ) which is made by preparing oil phase comprising emulsifier and silicone MQ resin.

[0004] Condensation polymers are any kind of polymers formed through a condensation reaction losing small molecules as by-products such as water or methanol, as opposed to addition polymers which involve the reaction of unsaturated monomers.

[0005] Types of condensation polymers include proteins, polyamides, polyacetals, polyesters and carbohydrates. The type of end product resulting from a condensation polymerization is dependent on the number of functional end groups of the monomer which can react.

[0006] Monomers with only one reactive group terminate a growing chain, and thus give end products with a lower molecular weight. Linear polymers are created using monomers with two reactive end groups and monomers with more than two end groups give three dimensional polymers which are crosslinked. [0007] It is desirable to incorporate silicone into polycondensation polymers to improve their properties. However it is sometimes difficult to incorporate silicone compounds, for example silicone compounds having a high molecular weight that have a high viscosity.

[0008] Thus, there exists a need to provide a process for incorporating silicone into condensation-type polymers to improve their properties.

BRIEF SUMMARY OF THE INVENTION

[0009] The present inventors have discovered that a co-polymer comprising silicone units can be prepared by a process comprising;

a) dispersing an emulsion comprising water, a silicone compound and a ethylene

oxide/propylene oxide block copolymer, with at least one monomer able to form condensation polymer by poly-condensation reaction and

b) reacting the silicone compound with the monomer to form a co-polymer containing silicone units.

[0010] The invention extends to the co-polymer produced by such process.

[0011] The invention further provides a method of improving mechanical, optical, or flame retardancy of a condensation polymer by dispersing an emulsion comprising a silicone compound and a ethylene oxide/propylene oxide block copolymer into monomers able to form the polycondensation polymer and let them react so as to form a co-polymer comprising silicone and polycondensation polymer.

[0012] The invention also extends to the use of an emulsion comprising a silicone compound and a ethylene oxide/propylene oxide block copolymer in a polycondensation polymerisation process.

DETAILED DESCRIPTION OF THE INVENTION

[0013] The silicone compound must contain a reactive moiety to participate in the polycondensation reaction. Preferably, the silicone compound is hydroxyl (of the formula -

OH) terminated, amino terminated or alkoxy terminated. The alkoxy moiety is of the formula -OR where R is an alkyl preferably methyl ethyl or propyl. The amino moiety is of the formula -NH2 or -NH(R) where R is an alkyl which may be substituted.

[0014] Silicone units are repeating-(Si-O-) units also known as siloxane units.

[0015] The condensation-type polymer is preferably a polymer different than silicone-based polymer.

[0016] Some examples of suitable amino-functional hydrocarbon groups are;

-CH₂CH₂NH₂, -CH2CH2CH2NH2, -CH₂CH(CH₃)NH₂, -CH2CH2CH2CH2NH2,

-CH2CH2CH2CH2CH2NH2, -CH2CH2CH2CH2CH2CH2NH2,-CH2CH₂NHCH3,

-CH2CH2CH2NHCH3, -CH₂CH(CH3)CH₂NHCH3, -CH2CH2CH2CH2NHCH3,

-CH2CH2NHCH2CH2NH2, - CH2CH2CH2NHCH2CH2NH2,

-CH2CH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2CH2NHCH2CH2CH2CH2NH2, -CH₂CH2NHCH2CH2NHCH_3! -CH₂CH2CH2NHCH2CH2CH2NHCH_3! -CH2CH2CH2CH2NHCH2CH2CH2CH2NHCH3, and

-CH2CH2NHCH2CH2NHCH2CH2CH2CH3.

[0017] Alternatively, the amino functional group is - CH2CH(CH3)CH2NHCH2CH2NH2. For example, the amino terminated silicone compound is Dimethyl, methyl

(aminoethylaminoisobutyl) siloxane.

[0018] Preferably, the silicone compound is a silicone gum or a silicone resin.

[0019] Preferably, the silicone compound has a kinetic viscosity greater than one million cSt at 25°C.

[0020] Preferably, the silicone compound is polydimethylsiloxane having a viscosity of at least 500 thousand cP at 0.01 Hz at 25°C.

[0021] Preferably, the silicone compound is alkoxy terminated polysiloxane comprising D^Me, D^Ph and/or D^MePh units.

[0022] Preferably, the silicone compound is hydroxyl terminated polydimethylsiloxane.

[0023] Preferably, the silicone compound is a MQ resin or a silsesquioxane resin.

[0024] The silicone compound preferably comprises -(R^a)2 Si -R^c- SiR^d _p(OR^b)₃-_p where each R^a independently represents a monovalent hydrocarbyl group, for example, an alkyl group, in particular having from 1 to 8 carbon atoms, (and is preferably methyl); each R^b is independently an alkyl and each R^d is independently an alkyl or alkoxy group in which the alkyl groups suitably have up to 6 carbon atoms; R^c is a divalent hydrocarbon group which may be interrupted by one or more siloxane spacers having up to six silicon atoms; and p has the value 0, 1 or 2.

[0025] Preferably, the siloxane compound comprises PDMS-CH2-CH2-Si(OR)3.

[0026] Preferably, the ethylene oxide/propylene oxide block copolymer is a

poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymer having the formula; HO(CH₂CH₂0)_m(CH₂CH(CH₃)0)n(CH₂CH₂0)_mH where m may vary from 50 to 400, and n may vary from 20 to 100.

[0027] Preferably, the ethylene oxide/propylene oxide block copolymer is a tetrafunctional poly(oxyethylene)-poly(oxypropylene) block copolymer having the average formula;

[HO(CH2CH20)_q(CH2CH(CH3)0)_r]2NCH2CH2N[(CH2CH(CH3)0)_r(CH2CH₂0)_qH]2 where q may vary from 50 to 400, and r may vary from 15 to 75.

[0028] Preferably, the condensation polymer is a protein, polyamide, polyacetal, polyester or carbohydrate.

[0029] As used herein, "parts" refers to parts by weight.

[0030] The silicone emulsion is preferably prepared by:

I) forming a dispersion of;

A) 100 parts of a silicone gum or a silicone resin, B) 5 to 100 parts of a ethylene oxide/propylene oxide block copolymer,

II) admixing a sufficient amount of water to the dispersion from step I) to form an

emulsion,

III) optionally, further shear mixing the emulsion.

A1 ) The Silicone Gum

[0031] Component A1 ) is a silicone gum. "Silicone gum" as used herein refers to predominately linear organopolysiloxanes having sufficiently high molecular weight (Mw) to provide kinetic viscosities greater than 500 thousand cSt at 25°C. While any

organopolysiloxane considered as a gum may be selected as component (A), typically the silicone gum is a diorganopolysiloxane gum with a molecular weight sufficient to impart a William's plasticity number of at least about 30 as determined by the American Society for Testing and Materials (ASTM) test method 926. The silicon-bonded organic groups of the diorganopolysiloxane may independently be selected from hydrocarbon or halogenated hydrocarbon groups. These may be specifically exemplified by alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl and hexyl; cycloalkyl groups, such as cyclohexyl and cycloheptyl; aryl groups having 6 to 12 carbon atoms, such as phenyl, tolyl and xylyl; aralkyl groups having 7 to 20 carbon atoms, such as benzyl and phenylethyl; and halogenated alkyl groups having 1 to 20 carbon atoms, such as 3,3,3- trifluoropropyl and chloromethyl. Thus, diorganopolysiloxane can be a homopolymer, a copolymer or a terpolymer containing such organic groups. Examples include

homopolymers comprising dimethylsiloxy units, homopolymers comprising 3,3,3- trifluoropropylmethylsiloxy units, copolymers comprising dimethylsiloxy units and phenylmethylsiloxy units, copolymers comprising dimethylsiloxy units and 3,3,3- trifluoropropylmethylsiloxy units, copolymers of dimethylsiloxy units and diphenylsiloxy units and interpolymers of dimethylsiloxy units, diphenylsiloxy units and phenylmethylsiloxy units, among others.

[0032] The silicon-bonded organic groups of the diorganopolysiloxane may also be selected from alkenyl groups having 1 to 20 carbon atoms, such as vinyl, allyl, butyl, pentyl, hexenyl, or dodecenyl. Examples include; dimethylvinylsiloxy-endblocked

dimethylpolysiloxanes; dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymers; dimethylvinylsiloxy-endblocked methylphenylpolysiloxanes; dimethylvinylsiloxy- endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers.

[0033] The silicon-bonded organic groups of the diorganopolysiloxane may also be selected from various organofunctional groups such as amino, amido, mercapto, or epoxy functional groups.

[0034] The molecular structure is also not critical and is exemplified by straight-chain and partially branched straight-chain structures, the linear systems being the most typical. [0035] The silicone gum used as component A) may also be a combination or mixture of any of the aforementioned polydiorganosiloxanes.

[0036] In one embodiment, the silicone gum is a hydroxy terminated polydimethylsiloxane gum having a viscosity of at least 20 million cP at 25°C at 0.01 Hz.

[0037] The silicone gum may be used in combination with other organopolysiloxanes. Organopolysiloxanes are polymers containing siloxane units independently selected from (R3S1O1/2), (R2S1O2/2), (RS1O3/2), or (S1O4/2) siloxy units, where R may be any monovalent organic group. When R is a methyl group in the (R3S1O1/2), (R2S1O2/2), (RS1O3/2), or (S1O4/2) siloxy units of an organopolysiloxane, the siloxy units are commonly referred to as M, D, T, and Q units respectively. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures can vary. For example organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins depending on the number and type of siloxy units in the average polymeric formula. R may be any monovalent organic group, alternatively R is a hydrocarbon group containing 1 to 30 carbons, alternatively R is an alkyl group containing 1 to 30 carbon atoms, or alternatively R is methyl.

[0038] The amount of the additional organopolysiloxane combined with the silicone gum may vary. Typically, 0.1 parts to 1000 parts by weight, alternatively 0.1 to 100 parts by weight of the additional organopolysiloxane is added for every 100 parts of the silicone gum.

[0039] In one embodiment, the silicone gum is combined with an aminofunctional

organopolysiloxane. The aminofunctional organopolysiloxanes may be characterized by having at least one of the R groups in the formula R_nSiO(_4-n)/2 be an amino functional group. The amino functional group may be present on any siloxy unit having an R substituent, that is, they may be present on any (R₃Si0_1/2), (R2S1O2/2), or (RSi0_3/2) unit, and is designated in the formulas herein as R^N. The amino-functional organic group R^N is illustrated by groups having the formula; -R³NHR⁴, -R³NR₂ ⁴ or -R³NHR³NHR⁴, wherein each R³ is independently a divalent hydrocarbon group having at least 2 carbon atoms, and R⁴ IS hydrogen or an alkyl group. Each R³ is typically an alkylene group having from 2 to 20 carbon atoms. R³ is illustrated by groups such as; -CH2CH2-, -CH2CH2CH2-, - CH2CHCH3-, -CH2CH2CH2CH2-, -CH₂CH(CH₃)CH₂-, -CH2CH2CH2CH2CH2-, - CH2CH2CH2CH2CH2CH2-, -CH₂CH2CH(CH2CH3)CH2CH₂CH2-,

-CH2CH2CH2CH2CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-.

The alkyl groups R⁴ are as illustrated above for R. When R⁴ is an alkyl group, it is typically methyl.

[0040] Some examples of suitable amino-functional hydrocarbon groups are;

-CH₂CH₂NH₂, -CH2CH2CH2NH2, -CH₂CH(CH₃)NH₂, -CH2CH2CH2CH2NH2, -CH₂CH2CH2CH2CH2NH_2! -C^C^C^C^C^Ch^Nh^,

-CH₂CH₂NHCH_3! -CH2CH₂CH2NHCH_3! -CH₂CH(CH3)CH2NHCH_3!

-CH₂CH2CH2CH2NHCH_3! -C^C^NHCh^Ch^NI-^, - CH₂CH2CH2NHCH2CH2NH_2! -CH₂CH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2CH2NHCH2CH2CH2CH2NH_2! -CH₂CH2NHCH2CH2NHCH_3! -CH₂CH2CH2NHCH2CH2CH₂NHCH_3!

-CH₂CH2CH2CH2NHCH2CH2CH2CH₂NHCH_3! and

-CH₂CH2NHCH2CH2NHCH2CH2CH₂CH₃.

[0041] Alternatively, the amino functional group is - CH2CH(CH₃)CH2NHCH2CH2NH2.

[0042] The aminofunctional organopolysiloxane used in combination with the silicone gum may be selected from those having the average formula;

[R₃SiOi_/2] [R₂Si0_2/2]_a[RR^NSi0_2/2]_b[R₃SiOi_/2]

where;

• a is 1-1000, alternatively 1 to 500, alternatively 1 to 200,

• b is 1-100, alternatively 1 to 50, alternatively 1 to 10,

· R is independently a monovalent organic group,

• alternatively R is a hydrocarbon containing 1- 30 carbon atoms,

• alternatively R is a monovalent alkyl group containing 1 - 12 carbons, or

• alternatively R is a methyl group;

• R^N is as defined above.

[0043] The aminofunctional organopolysiloxane used I combination with the silicone gum may also be a combination of any of the aforementioned aminofunctional organopolysiloxanes.

A2) The silicone resin

[0044] Component A2) is a silicone resin. As used herein, "silicone resin" refers to any organopolysiloxane containing at least one (RSi0_3/2), or (Si0_4/2) siloxy unit.

Organopolysiloxanes are polymers containing siloxy units independently selected from (R₃Si0_1/2), (R₂Si0_2/2), (RSi0_3/2), or (Si0_4/2) siloxy units, where R may be any organic group. These siloxy units are commonly referred to as M, D, T, and Q units respectively. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures vary depending on the number and type of siloxy units in the organopolysiloxane. "Linear" organopolysiloxanes typically contain mostly D or (R₂Si0_2/2) siloxy units, which results in polydiorganosiloxanes that are fluids of varying viscosity, depending on the "degree of polymerization" or DP as indicated by the number of D units in the polydiorganosiloxane. "Linear" organopolysiloxanes typically have glass transition temperatures (T_g) that are lower than 25°C. "Resin"

organopolysiloxanes result when a majority of the siloxy units are selected from T or Q siloxy units. When T siloxy units are predominately used to prepare an organopolysiloxane, the resulting organosiloxane is often referred to as a "silsesquioxane resin". When M and Q siloxy units are predominately used to prepare an organopolysiloxane, the resulting organosiloxane is often referred to as a "MQ resin". Alternatively, the formula for an organopolysiloxane may be designated by the average of the siloxy units in the

organopolysiloxane as follows; R_nSiO_(4-n)/2, where the R is independently any organic group, alternatively a hydrocarbon, or alternatively an alkyl group, or alternatively methyl. The value of n in the average formula may be used to characterize the organopolysiloxane. For example, an average value of n = 1 would indicate a predominate concentration of the (RS1O_3/2) siloxy unit in the organopolysiloxane, while n = 2 would indicate a predominance of (R₂S1O_2/2) siloxy units. As used herein, "organopolysiloxane resin" refers to those

organopolysiloxanes having a value of n less than 1.8 in the average formula R_nSiO₍₄-_n)/2, indicating a resin.

[0045] The silicone resin useful as component A) may independently comprise (i)

(R¹ ₃SiOi/₂)a , (ii) (R²2Si0₂/2)b , (iii) (R³Si0₃/2)_c , and (iv) (Si0_4/2)d siloxy units, providing there is at least one T or Q siloxy unit in the silicone resin molecule. The amount of each unit present in the silicone resin is expressed as a mole fraction (i.e. a, b, c, or d) of the total number of moles of all M, D, T, and Q units present in the silicone resin. Any such formula used herein to represent the silicone resin does not indicate structural ordering of the various siloxy units. Rather, such formulae are meant to provide a convenient notation to describe the relative amounts of the siloxy units in the silicone resin, as per the mole fractions described above via the subscripts a, b, c, and d. The mole fractions of the various siloxy units in the present organosiloxane block copolymers, as well as the silanol content, may be readily determined by ²⁹Si NMR techniques.

[0046] The silicone resin may also contain silanol groups (≡SiOH). The amount of silanol groups present on the silicone resin may vary from 0.1 to 35 mole percent silanol groups [≡SiOH], alternatively from 2 to 30 mole percent silanol groups [≡SiOH], alternatively from 5 to 20 mole percent silanol groups [≡SiOH]. The silanol groups may be present on any siloxy units within the silicone resin.

[0047] The molecular weight of the silicone resin is not limiting. The silicone resin may have an average molecular weight (M_w) of at least 1 ,000 g/mole, alternatively an average molecular weight of at least 2,000 g/mole alternatively an average molecular weight of at least 5,000 g/mole. The average molecular weight may be readily determined using Gel Permeation Chromatography (GPC) techniques.

[0048] In one embodiment, the silicone resin is a MQ silicone. The silicone resin may be a MQ resin comprising at least 80 mole% of siloxy units selected from (R¹ ₃Si0_1/2)_a and (Si0_4/2)_d units (that is a + d≥ 0.8), where R¹ is an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, with the proviso that at least 95 mole % of the R¹ groups are alkyl groups, a and d each have a value greater than zero, and the ratio of a/d is 0.5 to 1 .5.

[0049] The R¹ units of the MQ resin are independently an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group. The alkyl groups are illustrated by methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl. The aryl groups are illustrated by phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2- phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl with the aryl group typically being phenyl.

[0050] MQ resins suitable for use as component (A), and methods for their preparation, are known in the art. For example, U.S. Patent No. 2,814,601 to Currie et al., November 26, 1957, which is hereby incorporated by reference, discloses that MQ resins can be prepared by converting a water-soluble silicate into a silicic acid monomer or silicic acid oligomer using an acid. When adequate polymerization has been achieved, the resin is end-capped with trimethylchlorosilane to yield the MQ resin. Another method for preparing MQ resins is disclosed in U.S. Patent No. 2,857,356 to Goodwin, October 21 , 1958, which is hereby incorporated by reference. Goodwin discloses a method for the preparation of an MQ resin by the cohydrolysis of a mixture of an alkyl silicate and a hydrolyzable trialkylsilane

organopolysiloxane with water.

[0051] The MQ resins suitable as component A) in the present invention may contain D and T units. The MQ resins may also contain hydroxy groups. Typically, the MQ resins have a total weight % hydroxy content of 2-10 weight %, alternatively 2-5 weight %. The MQ resins can also be further "capped" wherein residual hydroxy groups are reacted with additional M groups.

[0052] In one embodiment, the silicone resin is a silsesquioxane resin. The silsesquioxane resin may be a silsesquioxane resin comprising at least 80 mole % of R³Si0_3/2 units, where R³ in the above trisiloxy unit formula is independently a Ci to C₂₀ hydrocarbyl, a carbinol group, or an amino group. As used herein, hydrocarbyl also includes halogen substituted hydrocarbyls. R³ may be an aryl group, such as phenyl, naphthyl, anthryl group.

Alternatively, R³ may be an alkyl group, such as methyl, ethyl, propyl, or butyl.

Alternatively, R³ may be any combination of the aforementioned alkyl or aryl groups.

Alternatively, R³ is phenyl, propyl, or methyl. In one embodiment, at least 40 mole % of the R³ groups are propyl, referred herein as T-propyl resins, since the majority of the siloxane units are T units of the general formula R³Si0_3/2 where at least 40 mole %, alternatively 50 mole %, or alternatively 90 mole % of the R³ groups are propyl. In another embodiment, at least 40 mole % of the R³ groups are phenyl, referred herein as T-phenyl resins, since the majority of the siloxane units are T units of the general formula R³Si0_3/2 where at least 40 mole %, alternatively 50 mole %, or alternatively 90 mole % of the R³ groups are phenyl. In yet another embodiment, R³ may be a mixture of propyl and phenyl. When R³ is a mixture of propyl and phenyl, the amounts of each in the resin may vary, but typically the R³ groups in the silsesquioxane resin may contain 60 - 80 mole percent phenyl and 20- 40 mole percent propyl.

[0053] Silsesquioxane resins are known in the art and are typically prepared by hydrolyzing an organosilane having three hydrolyzable groups on the silicon atom, such as a halogen or alkoxy group. Thus, silsesquioxane resins can be obtained by hydrolyzing

propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, or by co-hydrolyzing the aforementioned propylalkoxysilanes with various alkoxysilanes. Examples of these alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane,

methyltriisopropoxysilane, dimethyldimethoxysilane, and phenyltrimethoxysilane.

Propyltrichlorosilane can also be hydrolyzed alone, or in the presence of alcohol. In this case, co-hydrolyzation can be carried out by adding methyltrichlorosilane,

dimethyldichlorosilane, phenyltrichlorosilane, or similar chlorosilanes and

methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, or similar methylalkoxysilane. Alcohols suitable for these purposes include methanol, ethanol, n- propyl alcohol, isopropyl alcohol, butanol, methoxy ethanol, ethoxy ethanol, or similar alcohols. Examples of hydrocarbon-type solvents which can also be concurrently used include toluene, xylene, or similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons; and cyclohexane, or similar aliphatic hydrocarbons.

[0054] The silsesquioxane resins suitable in the present disclosure may contain M, D, and Q units, but typically at least 80 mole %, alternatively 90 mole % of the total siloxane units are T units. The silsesquioxane resins may also contain hydroxy and/or alkoxy groups. Typically, the silsesquioxane resins have a total weight % hydroxy content of 2-10 weight % and a total weight % alkoxy content of up to 20 weight %, alternatively 6-8 weight% hydroxy content and up to 10 weight % alkoxy content.

[0055] Representative, non-limiting examples of commercial silicone resins suitable as component A) include; silicone resins sold under the trademarks DOW CORNING® 840 Resin, DOW CORNING® 2-7466 Resin, DOW CORNING® 2-9138 Resin, DOW

CORNING® 2-9148 Resin, DOW CORNING® 2104 Resin , DOW CORNING® 2106

Resin, DOW CORNING® 217 Flake Resin, DOW CORNING® 220 Flake Resin, DOW

CORNING® 233 Flake Resin, DOW CORNING® 4-2136 Resin, Xiameter^® RSN-6018 Resin, Xiameter^® RSN-0217 Resin, Silres^® MK methyl silicone resin, Dow Corning^® MQ 1600 Resin.

[0056] As used herein, "silicone resin" also encompasses silicone-organic resins. Thus, silicone-organic resins includes silicone-organic copolymers, where the silicone portion contains at least one (RSi0_3/2), or (Si0_4/2) siloxy unit. The silicone portion of the silicone- organic resin may be any of the silisesquioxane or MQ resins as described above. The organic portion may be any organic polymer, such as those derived by free radical polymerization of one or more ethylenically unsaturated organic monomers. Various types of ethylenically unsaturated and/or vinyl containing organic monomers can be used to prepare the organic portion including; acrylates, methacrylates, substituted acrylates, substituted methacrylates, vinyl halides, fluorinated acrylates, and fluorinated

methacrylates, for example. Some representative compositions include acrylate esters and methacrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, decyl acrylate, lauryl acrylate, isodecyl methacrylate, lauryl methacrylate, and butyl methacrylate; substituted acrylates and methacrylates such as hydroxyethyl acrylate, perfluorooctyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxyethyl methacrylate; vinyl halides such as vinyl chloride, vinylidene chloride, and chloroprene; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl pyrrolidone; conjugated dienes such as butadiene and isoprene; vinyl aromatic compounds such as styrene and divinyl benzene; vinyl monomers such as ethylene;

acrylonitrile and methacrylonitrile; acrylamide, methacrylamide, and N-methylol acrylamide; and vinyl esters of monocarboxylic acids

[0057] The silicone resin selected as component A) may also be a combination(s) of any of the aforementioned silicone resins.

B) The Ethylene oxide/propylene oxide Block Copolymer

[0058] Component B) is an ethylene oxide/propylene oxide block copolymer. Component B) may be selected from those ethylene oxide/propylene oxide block copolymers known to have surfactant behaviour. Typically, the ethylene oxide/propylene oxide block copolymers useful as component B) are surfactants. They have preferably an HLB of at least 12, alternatively, at least 15, or alternatively at least 18.

[0059] The molecular weight of the ethylene oxide/propylene oxide block copolymer may vary, but typically is at least 4,000 g/mol, alternatively at least 8,000 g/mol, or at least 12,000 g/mol.

[0060] The amounts of ethylene oxide (EO) and propylene oxide (PO) present in the ethylene oxide/propylene oxide block copolymer may vary, but typically, the amount of EO may vary from 50 percent to 80 percent, or alternatively from 60 percent to about 85 percent, or alternatively from 70 percent to 90 percent.

[0061] In one embodiment, component B) is a poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymer. Poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. They are nonionic triblock copolymers composed of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of

polyoxyethylene (poly(ethylene oxide)).

[0062] Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF (Florham Park, NJ) and are sold under the tradename PLURONIC®. Representative, non-limiting examples suitable as component (B) include; PLURONIC® F127, PLURONIC® F98, PLURONIC® F88, PLURONIC® F87, PLURONIC® F77 and PLURONIC® F68, and PLURONIC® F-108.

[0063] In a further embodiment, the poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymer has the formula;

HO(CH₂CH₂0)_m(CH₂CH(CH₃)0)_n(CH₂CH₂0)_mH

where;

• the subscript "m" may vary from 50 to 400, or

• alternatively from 100 to 300,

• and the subscript "n" may vary from 20 to 100, or

· alternatively from 25 to 100.

[0064] In one embodiment, component B) is a tetrafunctional poly(oxyethylene)- poly(oxypropylene) block copolymer derived from the sequential addition of propylene oxide and ethylene oxide to ethylene diamine. These tetra-functional block copolymers are also commonly known as Poloxamines. The tetrafunctional poly(oxyethylene)- poly(oxypropylene) block copolymer may have the average formula;

[HO(CH₂CH₂0)_q(CH₂CH(CH₃)0)_r]₂NCH₂CH₂N[(CH₂CH(CH₃)0)_r(CH₂CH₂0)_qH]₂

where;

• the subscript "q" may vary from 50 to 400, or

• alternatively from 100 to 300,

· and the subscript "r" may vary from 15 to 75, or

• alternatively from 20 to 50.

[0065] Tetrafunctional poly(oxyethylene)-poly(oxypropylene) block copolymers are commercially available from BASF (Florham Park, NJ) and are sold under the tradename TETRONIC®. Representative, non-limiting examples suitable as component (B) include; TETRONIC® 908, TETRONIC® 1 107, TETRONIC® 1307, TETRONIC® 1508 and

TETRONIC® 1504. The amount of components A) and B) combined in step I) of forming the emulsion are preferably as follows;

A) 100 parts of a silicone gum, and

B) 5 to 100 parts, alternatively 10 to 40 parts, or alternatively 10 to 25 of the ethylene oxide/propylene oxide block copolymer.

[0066] In one embodiment, the dispersion formed in step I) consists essentially of components A) and B) as described above. In this embodiment, no additional surfactants or emulsifiers are added in step I). Furthermore, no solvents are added for the purpose of enhancing formation of an emulsion. As used herein, the phrase "essentially free of "solvents" means that solvents are not added to components A) and B) in order to create a mixture of suitable viscosity that can be processed on typical emulsification devices. More specifically, "solvents" as used herein is meant to include any water immiscible low molecular weight organic or silicone material added to the non-aqueous phase of an emulsion for the purpose of enhancing the formation of the emulsion, and is subsequently removed after the formation of the emulsion, such as evaporation during a drying or film formation step. Thus, the phrase "essentially free of solvent" is not meant to exclude the presence of solvent in minor quantities in process or emulsions of the present invention. For example, there may be instances where the components A) and B) may contain minor amounts of solvent as supplied commercially. Small amounts of solvent may also be present from residual cleaning operations in an industrial process. Preferably, the amount of solvent present in the premix should be less than 2% by weight of the mixture, and most preferably the amount of solvent should be less than 1 % by weight of the mixture.

[0067] The dispersion of step (I) may be prepared by combining components A) and B) and further mixing the components to form a dispersion. The resulting dispersion may be considered as a homogenous mixture of the two components. The present inventors have unexpectedly found that certain ethylene oxide/propylene oxide block copolymers readily disperse with silicone gum compositions, and hence enhance the subsequent formation of emulsion compositions thereof. The present inventors believe other nonionic and/or anionic surfactants, typically known for preparing silicone emulsions, do not form such dispersions or homogeneous mixtures upon mixing with a silicone gum (at least not in the absence of a solvent or other substance to act as a dispersing medium). While not wishing to be limited to any theory, the inventors believe the discovery of the present ethylene oxide/propylene oxide block copolymers to form such dispersions with silicone gums, provides emulsion compositions of silicone gums without the presence of undesirable solvents, or requiring elaborate handling/mixing techniques.

[0068] Mixing can be accomplished by any method known in the art to effect mixing of high viscosity materials. The mixing may occur either as a batch, semi-continuous, or continuous process. Mixing may occur, for example using, batch mixing equipments with medium / low shear include change-can mixers, double-planetary mixers, conical-screw mixers, ribbon blenders, double-arm or sigma-blade mixers; batch equipments with high- shear and high-speed dispersers include those made by Charles Ross & Sons (NY),

Hockmeyer Equipment Corp. (NJ); batch mixing equipment such as those sold under the tradename Speedmixer®; batch equipments with high shear actions include Banbury-type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX). Illustrative examples of continuous mixers / compounders include extruders single-screw, twin-screw, and multi-screw extruders, co-rotating extruders, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ), and Leistritz (NJ); twin-screw counter- rotating extruders, two-stage extruders, twin-rotor continuous mixers, dynamic or static mixers or combinations of these equipments.

[0069] The process of combining and mixing components A) and B) may occur in a single step or multiple step process. Thus, components A) and B) may be combined in total, and subsequently mixed via any of the techniques described above. Alternatively, a portion(s) of components A) and B) may first be combined, mixed, and followed by combining additional quantities of either or both components and further mixing. One skilled in the art would be able to select optimal portions of components A) and B) for combing and mixing, depending on the selection of the quantity used and the specific mixing techniques utilized to perform step I) to provide a dispersion of components A) and B).

[0070] Step II of the process involves admixing sufficient water to the mixture of step I to form an emulsion. Typically 5 to 700 parts water are mixed for every 100 parts of the step I mixture to form an emulsion. In one embodiment the emulsion formed is a water continuous emulsion. Typically, the water continuous emulsion has dispersed particles of the silicone gum from step I, and having an average particle size less than 150 μηη.

[0071] The amount of water added in step II) can vary from 5 to 700 parts per 100 parts by weight of the mixture from step I. The water is added to the mixture from step I at such a rate so as to form an emulsion of the mixture of step I. While this amount of water can vary depending on the selection of the amount of silicone gum present and the specific ethylene oxide/propylene oxide block copolymer used, generally the amount of water is from 5 to 700 parts per 100 parts by weight of the step I mixture, alternatively from 5 to 100 parts per 100 parts by weight of the step I mixture, or alternatively from 5 to 70 parts per 100 parts by weight of the step I mixture.

[0072] Typically the water is added to the mixture from step I in incremental portions, whereby each incremental portion comprises less than 30 weight % of the mixture from step I and each incremental portion of water is added successively to the previous after the dispersion of the previous incremental portion of water, wherein sufficient incremental portions of water are added to form an emulsion.

[0073] Alternatively, a portion or all the water used in step I) may be substituted with various hydrophilic solvents that are soluble with water such as low molecular weight alcohols, ethers, esters or glycols. Representative non-limiting examples include low molecular weight alcohols such as methanol, ethanol, propanol, isopropanol and the like; low molecular weight ethers such as di(propyleneglycol) mono methyl ether, di(ethyleneglycol) butyl ether, di(ethyleneglycol) methyl ether, di(propyleneglycol) butyl ether, di(propyleneglycol) methyl ether acetate, di(propyleneglycol) propyl ether, ethylene glycol phenyl ether, propylene glycol butyl ether, 1 -methoxy-2-propanol, 1-methoxy-2- propyl acetate, propylene glycol propyl ether, 1 -phenoxy-2-propanol, tri(propyleneglycol) methyl ether and tri(propyleneglycol) butyl ether, and other like glycols.

[0074] Mixing in step (II) can be accomplished by any method known in the art to affect mixing of high viscosity materials. The mixing may occur either as a batch, semi- continuous, or continuous process. Any of the mixing methods as described for step (I), may be used to affect mixing in step (II). Typically, the same equipment is used to effect mixing in steps I) and II).

[0075] Optionally, the water continuous emulsion formed in step (II) may be further sheared according to step (I II) to reduce particle size and/or improve long term storage stability. The shearing may occur by any of the mixing techniques discussed above.

[0076] The emulsion products resulting from the present process may be an oil/water emulsion, a water/oil emulsion, a multiple phase or triple emulsion.

[0077] In one embodiment, the emulsion products produced by the present process are oil/water emulsions. The oil/water emulsion may be characterized by average volume particle of the dispersed silicone gum (oil) phase in a continuous aqueous phase. The particle size may be determined by laser diffraction of the emulsion. Suitable laser diffraction techniques are well known in the art. The particle size is obtained from a particle size distribution (PSD). The PSD can be determined on a volume, surface, length basis. The volume particle size is equal to the diameter of the sphere that has the same volume as a given particle. The term Dv represents the average volume particle size of the dispersed particles. Dv 50 is the particle size measured in volume corresponding to 50% of the cumulative particle population. In other words if Dv 50 = 10 μηη, 50% of the particle have an average volume particle size below 10 μηη and 50% of the particle have a volume average particle size above 10 μηη. Dv 90 is the particle size measured in volume corresponding to 90% of the cumulative particle population.

[0078] The average volume particle size of the dispersed siloxane particles in the oil/water emulsions is between 0.1 μηη and 150 μηη; or between 0.1 μηη and 30 μηη; or between 0.3 μηη and 5.0 μηι.

[0079] Silicone gum content of the present emulsion may vary from 0.5 weight percent to 95 weight percent, alternatively from 20 weight percent to 80 weight percent, or alternatively from 40 weight percent to 60 weight percent.

[0080] Additional additives and components may also be included in the emulsion compositions, such as preservatives, freeze/thaw additives, and various thickeners. Condensation polymers

[0081] Condensation polymers may be thermoplastics or thermosets.

[0082] Dehydration synthesis often involves joining monomers with an -OH (hydroxyl) group and a freely ionized -H on either end (such as a hydrogen from the -NH₂ in nylon or proteins). Normally, one, two or more different monomers are used in the reaction. The bonds between the hydroxyl group, the hydrogen atom and their respective atoms break forming water from the hydroxyl and hydrogen, and the polymer.

[0083] Polyester is created through ester linkages between monomers, which involve the functional groups carboxyl and hydroxyl (an organic acid and an alcohol monomer).

[0084] Nylon is another common condensation polymer. It can be manufactured by reacting di-amines with carboxyl derivatives. In this example the derivative is a di- carboxylic acid, but di-acyl chlorides are also used. Another approach used is the reaction of di-functional monomers, with one amine and one carboxylic acid group on the same molecule:

[0085] The carboxylic acids and amines link to form peptide bonds, also known as amide groups. Proteins are condensation polymers made from amino acid monomers.

Carbohydrates are also condensation polymers made from sugar monomers such as glucose and galactose.

[0086] Condensation polymerization is occasionally used to form simple hydrocarbons. This method, however, is expensive and inefficient, so the addition polymer of ethene (polyethylene) is generally used.

[0087] Condensation polymers, unlike addition polymers, may be biodegradable. The peptide or ester bonds between monomers can be hydrolysed by acid catalysts or bacterial enzymes breaking the polymer chain into smaller pieces.

[0088] The most commonly known condensation polymers are proteins, fabrics such as nylon, silk, or polyester.

[0089] Proteins are polymer chains made of amino acids linked together by peptide bonds. Amino acids can be divided into either essential amino acids or non-essential amino acids. The essential amino acids, which must be obtained from food sources, are leucine, isoleucine, valine, lysine, threonine, tryptophan, methionine, phenylalanine and histidine. On the other hand, non-essential amino acids can be made by the body from other amino acids. The non-essential amino acids are arginine, alanine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, proline, serine, and tyrosine.

[0090] The words protein, polypeptide, and peptide are a little ambiguous and can overlap in meaning. Protein is generally used to refer to the complete biological molecule in a stable conformation, whereas peptide is generally reserved for a short amino acid oligomers often lacking a stable three-dimensional structure. However, the boundary between the two is not well defined and usually lies near 20-30 residues. Polypeptide can refer to any single linear chain of amino acids, usually regardless of length, but often implies an absence of a defined conformation

[0091] A peptide bond (amide bond) is a covalent chemical bond formed between two molecules when the carboxyl group of one molecule reacts with the amino group of the other molecule, causing the release of a molecule of water (H₂0), hence the process is a dehydration synthesis reaction (also known as a condensation reaction), and usually occurs between amino acids. The resulting C(0)NH bond is called a peptide bond, and the resulting molecule is an amide. The four-atom functional group -C(=0)NH- is called a peptide link. Polypeptides and proteins are chains of amino acids held together by peptide bonds, as is the backbone of PNA.

[0092] A polyamide is a polymer containing monomers of amides joined by peptide bonds. They can occur both naturally and artificially, examples being proteins, such as wool and silk, and can be made artificially through step-growth polymerization or solid-phase synthesis, examples being nylons, aramids, and sodium poly(aspartate). Polyamides are commonly used in textiles, automotives, carpet and sportswear due to their extreme durability and strength.

[0093] According to the composition of their main chain, polyamides are classified as follows:

• homopolymers:

o PA 6 : [NH-(CH₂)₅-CO]_n made from ε-Caprolactam ;

o PA 66 : [NH-(CH2)6-NH-CO-(CH₂)4-CO]_n made from hexamethylenediamine and adipic acid;

· copolymers: o PA 6/66 : [NH-(CH2)6-NH-CO-(CH2)4-CO]n-[NH-(CH2)5-CO]m made from caprolactam, hexamethylenediamine and adipic acid ;

o PA 66/610:

[NH-(CH2)6-NH-CO-(CH2)4-CO]n-[NH-(CH2)6-NH-CO-(CH2)8-CO]m made from hexamethylenediamine, adipic acid and sebacic acid.

[0095] According to their crystallinity, polyamides can be:

• semi-crystalline:

o high crystallinity : PA46 et PA 66 ;

o low crystallinity : PA mXD6 made from m-xylylenediamine and adipic acid; · amorphous: PA 61 made from hexamethylenediamine and isophthalic acid.

[0096] According to this classification, PA66, for example, is an aliphatic semi-crystalline homopolyamide.

[0097] The amide link is produced from the condensation reaction of an amino group and a carboxylic acid or acid chloride group. A small molecule, usually water, or hydrogen chloride, is eliminated.

[0098] The amino group and the carboxylic acid group can be on the same monomer, or the polymer can be constituted of two different bifunctional monomers, one with two amino groups, the other with two carboxylic acid or acid chloride groups.

[0099] Amino acids can be taken as examples of single monomer (if the difference between R groups is ignored) reacting with identical molecules to form a polyamide.

[0100] Polyoxymethylene (POM), also known as acetal, polyacetal, and polyformaldehyde, is an engineering thermoplastic used in precision parts that require high stiffness, low friction and excellent dimensional stability.

[0101] First synthesized by DuPont research chemists around 1952, some well known products are Delrin, Celcon and Hostaform.

[0102] POM is characterized by its high strength, hardness and rigidity to -40°C. POM is intrinsically opaque white, due to its high crystalline composition, but it is available in all colours. POM has a density of p = 1.410 - 1 .420 g / cm³.

[0103] POM homopolymer is a semi-crystalline polymer (75-85% crystalline) with a melting point of 175° Celsius. The POM copolymer has a slightly lower melting point of 162 - 173° Celsius.

[0104] POM is a tough material with a very low coefficient of friction. However, it is susceptible to polymer degradation catalyzed by acids, which is why both polymer types are stabilized. Both homopolymer and copolymer have chain end groups (introduced via end capping) which resist depolymerization. With the copolymer, the second unit normally is a C2 (ethylene glycol) or C4 (1 ,4-butanediol) unit, which is introduced via its cyclic acetal (which can be made from the diol and formaldehyde) or cyclic ether (e.g. ethylene oxide). These units resist chain cleavage, because the O-linkage is now no longer an acetal group, but an ether linkage, which is stable to hydrolysis. POM is sensitive to oxidation, and an anti-oxidant is normally added to moulding grades of the material.

[0105] POM advantages:

· High abrasion resistance

• Low coefficient of friction

• High heat resistance

• Good electrical and dielectric properties

• Low water absorption

[0106] To make polyoxymethylene homopolymer, anhydrous formaldehyde must be generated. The principal method is by reaction of the aqueous formaldehyde with an alcohol to create a hemiformal, dehydration of the hemiformal/water mixture (either by extraction or vacuum distillation) and release of the formaldehyde by heating the hemiformal. The formaldehyde is then polymerized by anionic catalysis and the resulting polymer stabilized by reaction with acetic anhydride. A typical example is DuPont's Delrin.

[0107] To make polyoxymethylene copolymer, formaldehyde is generally converted to trioxane. This is done by acid catalysis (either sulfuric acid or acidic ion exchange resins) followed by purification of the trioxane by distillation and/or extraction to remove water and other active hydrogen containing impurities. Typical copolymers are Hostaform from Ticona and Ultraform from BASF.

[0108] The co-monomer is typically dioxolane but ethylene oxide can also be used.

Dioxolane is formed by reaction of ethylene glycol with aqueous formaldehyde over an acid catalyst. Other diols can also be used.

[0109] Trioxane and Dioxolane are polymerized using an acid catalyst, often boron trifluoride etherate, BF₃ OEt₂. The polymerization can take place in a non-polar solvent (in which case the polymer forms as a slurry) or in neat trioxane (e.g. in an extruder). After polymerization, the acidic catalyst must be deactivated and the polymer stabilized by melt or solution hydrolysis in order to remove the unstable end groups.

[0110] Stable polymer is melt compounded, adding thermal and oxidative stabilizers and optionally lubricants and miscellaneous fillers.

[0111] Aramid (pictured below) is made from two different monomers 1 ,4-phenyl-diamine

(para-phenylenediamine) and terephthaloyl chloride which continuously alternate to form the polymer and is an aromatic polyamide.

[0112] Polyester is a category of polymers which contain the ester functional group in their main chain. Although there are many polyesters, the term "polyester" as a specific material most commonly refers to polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in the cutin of plant cuticles, as well as synthetics through step-growth polymerization such as polycarbonate and polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not.

[0113] Depending on the chemical structure, polyester can be a thermoplastic or thermoset; however, the most common polyesters are thermoplastics.

[0114] Fabrics woven or knitted from polyester thread or yarn are used extensively in apparel and home furnishings, from shirts and pants to jackets and hats, bed sheets, blankets, upholstered furniture and computer mouse mats. Industrial polyester fibres, yarns and ropes are used in tyre reinforcements, fabrics for conveyor belts, safety belts, coated fabrics and plastic reinforcements with high-energy absorption. Polyester fibre is used as cushioning and insulating material in pillows, comforters and upholstery padding.

Polyesters are also used to make bottles, films, tarpaulin, canoes, liquid crystal displays, holograms, filters, dielectric film for capacitors, film insulation for wire and insulating tapes. Polyesters are widely used as a finish on high-quality wood products such as guitars, pianos and vehicle/yacht interiors. Thixotropic properties of spray-applicable polyesters make them ideal for use on open-grain timbers, as they can quickly fill wood grain, with a high-build film thickness per coat. Cured polyesters can be sanded and polished to a high- gloss, durable finish.

[0115] While synthetic clothing in general is perceived by many as having a less natural feel compared to fabrics woven from natural fibres (such as cotton and wool), polyester fabrics can provide specific advantages over natural fabrics, such as improved wrinkle resistance, durability and high color retention. As a result, polyester fibres are sometimes spun together with natural fibres to produce a cloth with blended properties. Synthetic fibres also can create materials with superior water, wind and environmental resistance compared to plant-derived fibres.

[0116] Liquid crystalline polyesters are among the first industrially used liquid crystal polymers. They are used for their mechanical properties and heat-resistance. These traits are also important in their application as an abradable seal in jet engines.

[0117] Polyesters as thermoplastics may change shape after the application of heat. While combustible at high temperatures, polyesters tend to shrink away from flames and self- extinguish upon ignition. Polyester fibres have high tenacity and E-modulus as well as low water absorption and minimal shrinkage in comparison with other industrial fibres.

[0118] Unsaturated polyesters (UPR) are thermosetting resins. They are used as casting materials, fibreglass laminating resins and non-metallic auto-body fillers. Fibreglass- reinforced unsaturated polyesters find wide application in bodies of yachts and as body parts of cars.

[0119] According to the composition of their main chain, polyesters can be: Composition Number of Examples of polyesters Examples of manufacturing of the main repeating units methods

chain

Aliphatic Homopolymer Polyglycolide or Polvcondensation of qlvcolic

Polyglycolic acid (PGA) acid

Polylactic acid (PLA) Ring-opening polymerization of lactide

Polycaprolactone (PCL) Ring-opening polymerization of caprolactone

Copolymer Polyethylene adipate

(PEA)

Polynydroxyalkanoate

(PHA)

Semi-aromatic Copolymer Polyethylene Polycondensation of

tereohtalate (PET) terephthalic acid with

ethylene glycol

Polybutylene Polycondensation of terephthalate (PBT) terephthalic acid with 1 ,4- butanediol

Polytrimethylene Polycondensation of terephthalate (PTT) terephthalic acid with 1 ,3- propanediol

Polyethylene Polycondensation of at least naphthalate (PEN) one naphthalene dicarboxylic acid with ethylene glycol

Aromatic Copolymer Vectran Polycondensation of Φ;

hvdroxvbenzoic acid and 6- hydroxynaphthalene-2- carboxylic acid

[0120] Increasing the aromatic parts of polyesters increases their glass transition temperature, melting temperature, thermal stability, chemical stability.

[0121] Polyesters can also be telechelic oligomers like the polycaprolactone diol (PCL) and the polyethylene adipate diol (PEA). They are then used as prepolymers.

[0122] Polyester is a synthetic polymer made of purified terephthalic acid (PTA) or its dimethyl ester dimethyl terephthalate (DMT) and monoethylene glycol (MEG). With 18% market share of all plastic materials produced, it ranges third after polyethylene (33.5%) and polypropylene (19.5%). [0123] The main raw materials are described as follows:

Purified terephthalic acid - PTA - CAS-No.: 100-21-0

Synonym: 1 ,4 benzenedicarboxylic acid,

Sum formula; C₆H₄(COOH)2 , mol weight: 166.13

Dimethylterephthalate - DMT - CAS-No: 120-61-6

Synonym: 1 ,4 benzenedicarboxylic acid dimethyl ester

Sum formula C₆H₄(COOCH₃)2 , mol weight: 194.19

Mono Ethylene Glycol - MEG - CAS No.: 107-21-1

Synonym: 1 ,2 ethanediol

Sum formula: C₂H₆02 , mol weight: 62,07

[0124] To make a polymer of high molecular weight a catalyst is needed. The most common catalyst is antimony trioxide (or antimony tri acetate). Antimony trioxide - ATO - CAS-No.: 1309-64-4 Molecular weight: 291 .51 Sum formula:

Sb₂0₃

[0125] Polyester is described as follows: Polyethylene Terephthalate CAS-No.: 25038-59-9 Synonym/abbreviations: polyester, PET, PES Sum Formula: H-[C₁₀H₈O₄]-n=60-120 OH, molecular unit weight: 192.17

[0126] After the first stage of polymer production in the melt phase, the product stream divides into two different application areas which are mainly textile applications and packaging applications.

Textured Yarn; FDY = Fully Drawn Yarn; CSD = Carbonated Soft Drink; A-PET =

Amorphous Polyester Film; BO-PET = Biaxial Oriented Polyester Film;

[0127] In order to produce the polyester melt with a high efficiency, high-output processing steps like staple fibre (50-300 tonnes/day per spinning line) or POY /FDY (up to 600 tonnes/day split into about 10 spinning machines) are meanwhile more and more vertically integrated direct processes. This means the polymer melt is directly converted into the textile fibres or filaments without the common step of pelletizing.

[0128] Synthesis of polyesters is generally achieved by a polycondensation reaction. The general equation for the reaction of a diol with a diacid is: (n+1 ) R(OH)₂ + n R^'(COOH)₂→ HO[ROOCR^'COO]_nROH + 2n H₂0

Azeotrope esterification

[0129] In this classical method, an alcohol and a carboxylic acid react to form a carboxylic ester. To assemble a polymer, the water formed by the reaction must be continually removed by azeotrope distillation.

Alcoholic transesterification

[0130] Main article: Transesterification

[0131] Transesterification: An alcohol-terminated oligomer and an ester-terminated oligomer condense to form an ester linkage, with loss of an alcohol. R and R' are the two oligomer chains, R" is a sacrificial unit such as a methyl group (methanol is the by-product of the esterification reaction).

Acylation (HCI method)

[0132] The acid begins as an acid chloride, and thus the polycondensation proceeds with emission of hydrochloric acid (HCI) instead of water. This method can be carried out in solution or as an enamel.

Silyl method

[0133] In this variant of the HCI method, the carboxylic acid chloride is converted with the trimethyl silyl ether of the alcohol component and production of trimethyl silyl chloride is obtained.

Acetate method (esterification)

Silyl acetate method

Ring-opening polymerization

[0134] Aliphatic polyesters can be assembled from lactones under very mild conditions, catalyzed anionically, cationically or metallorganically. A number of catalytic methods for the copolymerization of epoxides with cyclic anhydrides have also recently been shown to provide a wide array of functionalized polyesters, both saturated and unsaturated.

Cross-linking

[0135] Unsaturated polyesters are thermosetting resins. They are generally copolymers prepared by polymerizing one or more diol with saturated and unsaturated dicarboxylic acids (maleic acid, fumaric acid) or their anhydrides. The double bond of unsaturated polyesters reacts with a vinyl monomer mainly the styrene, resulting in a 3-D cross-linked structure. This structure acts as a thermoset. The cross-linking is initiated through an exothermic reaction involving an organic peroxide, such as methyl ethyl ketone peroxide or benzoyl peroxide.

EXAMPLES

[0136] The following examples are included to demonstrate certain embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. All percentages are in wt. %. All measurements were conducted at 23°C unless indicated otherwise.

Example 1 - Emulsification of Silicone Gum Using Pluronic^® F-88

[0137] First, 15g of silicone gum (Dow Corning^® SGM-36, a hydroxy terminated

polydimethylsiloxane) was weighed into a Max 40 cup along with 1.5g of Pluronic^® F-88 nonionic surfactant and 10g of 3mm glass beads. The cup was closed and placed inside a DAC-150 SpeedMixer^® and the cup was spun at maximum speed (3450 RPM) for 2 minutes. The cup was opened and the mixture, now very warm, had become a creamy white paste that easily flowed when mixed with a spatula. The walls of the cup were scraped with a spatula and the cup was spun again at maximum speed for 1 minute. Then, 0.88g of water was added to the cup and the cup was spun for 30 seconds at maximum speed. An additional 1.2g of water was added and the cup was again spun for 30 seconds at maximum speed. Two more water additions were made, one of 2.5g and the other 3.92g with the cup being spun for 20 seconds after each water addition. The milky white mixture was now finished and it consisted of an o/w emulsion of silicone gum having a silicone content of 60 percent by weight. Particle size of the emulsion was determined using a Malvern Mastersizer S (version 2.19) and the results were: Dv50 = 6.93um, Dv90 = 13.24um.

Example 2 - Emulsification of Silicone Resin using Pluronic^® F-108

[0138] The following were weighed into a Max 100 cup in the following order: 35g silicone flake resin (Xiameter^® RSN-6018 Resin) having a number average molecular weight of 1200 and a specific gravity of 1.25, 16g of 3mm spherical glass beads (Fisher) and 7g of Pluronic^® F-108 nonionic surfactant. The cup was closed and placed into a DAC-150 SpeedMixer^® and the cup was spun at maximum speed (3450 RPM) for two minutes. The cup was opened and inspected. The mixture, which had become very warm, had taken on a creamy white appearance. The cup was closed and allowed to stand undisturbed for five minutes in order for the mixture to cool slightly. The cup was placed back in the mixer and spun for an additional 1 minute at maximum speed. The mixture was diluted with 28g of deionized (Dl) water in five increments by adding aliquots of water and spinning the cup for 25 seconds after addition of each aliquot. The increments of water were as follows: 2g, 3g, 5g, 8g and 10g. Following the last dilution, the resulting composition consisted of an o/w emulsion of silicone resin having a silicone content of 50 percent by weight. Particle size of the emulsion was measured using a Malvern^® Mastersizer 2000 and found to be: Dv50 = 0.56μη-ι; Dv90 = 0.94μηι.

Claims

1 . A process for forming a co-polymer containing silicone comprising;

a) dispersing an emulsion comprising water, a silicone compound and a ethylene oxide/propylene oxide block copolymer, with at least one monomer able to form condensation polymer by poly-condensation reaction and

b) reacting the silicone compound with the monomer to form a co-polymer

containing silicone units.

2. The process of claim 1 wherein the silicone compound is hydroxyl, amino or alkoxy terminated.

3. The process of claim 1 or 2 wherein the silicone compound is a silicone gum or a silicone resin.

4. The process of any preceding claim wherein the silicone compound has a kinetic viscosity greater than one million cSt at 25°C.

5. The process of any preceding claim wherein the silicone compound is

polydimethylsiloxane having a viscosity of at least 500 thousand cP at 0.01 Hz at 25°C.

6. The process of any preceding claim wherein the silicone compound is alkoxy

terminated polysiloxane comprising DMe, DPh and/or DMePh units.

7. The process of any preceding claim wherein the silicone compound is hydroxyl terminated polydimethylsiloxane.

8. The process of any preceding claim wherein the silicone compound is a MQ resin or a silsequioxane resin.

9. The process of any preceding claim wherein the silicone compound comprises

-(Ra)2Si -Rc- SiRdp(ORb)3-p where each Ra independently represents a monovalent hydrocarbyl group, for example, an alkyl group, in particular having from 1 to 8 carbon atoms, (and is preferably methyl); each Rb is independently an alkyl and each Rd is independently an alkyl or alkoxy group in which the alkyl groups suitably have up to 6 carbon atoms; Rc is a divalent hydrocarbon group which may be interrupted by one or more siloxane spacers having up to six silicon atoms; and p has the value 0, 1 or 2.

10. The process of any preceding claim wherein the siloxane compound comprises PDMS-CH2-CH2-Si(OR)3.

1 1. The process of any preceding claim wherein the ethylene oxide/propylene oxide block copolymer is a poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri- block copolymer having the formula;

HO(CH2CH20)m(CH2CH(CH3)0)n(CH2CH20)mH where m may vary from 50 to 400, and n may vary from 20 to 100.

12. The process of any preceding claim wherein the ethylene oxide/propylene oxide block copolymer is a tetrafunctional poly(oxyethylene)-poly(oxypropylene) block copolymer having the average formula;

[HO(CH2CH20)q(CH2CH(CH3)0)r]2NCH2CH2N[(CH2CH(CH3)0)r(CH2CH20)qH]2 where q may vary from 50 to 400, and r may vary from 15 to 75.

13. The process according to any preceding claim wherein the condensation polymer is a protein, polyamide, polyacetal, polyester or carbohydrate.

14. The co-polymer obtained by a process according to any preceding claim.

15. A method of improving mechanical, optical, or flame retardancy of a condensation polymer by dispersing an emulsion comprising a silicone compound and a ethylene oxide/propylene oxide block copolymer into monomers able to form the

polycondensation polymer and let them react so as to form a co-polymer comprising silicone and polycondensation polymer.

16. Use of an emulsion comprising a silicone compound and a ethylene oxide/propylene oxide block copolymer in a polycondensation polymerisation process.