SA515360973B1 - Acrylic grafted polyether resins based on phenol stearic acid and coating compositions formed therefrom - Google Patents

Abstract

Coating compositions can be prepared from an acrylic grafted polyether resin, wherein the smallest difunctional hydroxyl phenyl segment used to form the acrylic grafted polyether resin has a molecular weight greater than about 500, and wherein the smallest difunctional hydroxyl phenyl segment used to form the acrylic grafted polyether resin does not comprise two or more non-impaired hydroxyl groups attached to two or more different five-membered or six-membered carbon atom rings in a segment having a molecular weight less than about 500. The acrylic grafted polyether resin can be prepared by reacting a dihydroxyl compound and/or a diamine compound with a phenol stearic acid compound to produce a diphenol, reacting the diphenol with a diglycidyl ether compound to form a polyether resin, and mixing the polyether resin with an ethylenically unsaturated monomer component in the presence of an initiator to form the acrylic grafted polyether resin.

Description

1 Acrylic grafted polyether resins based on phenol stearic acid and coating compositions formed therefrom Full Description

BACKGROUND OF THE INVENTION The present invention relates to bisphenol-A free polyether resins zl acrylic grafted on phenol stearic acid coating compositions with polyether resins © acrylic grafted polyether resins Methods for coating substrates using coating compositions; and substrates coated using paint formulations. Many of the coating formulations currently used in the packaging coatings industry do not harden well when mixed with phenolic resin crosslinkers. Melamine and benzoguanamine have been used in the form of crosslinkers -20 | 0 with phenolic resins to bind polyesters and improve stiffness; However, in the manufacture of packing coatings it is desirable to avoid Jie ctriazines, melamine, and benzoguanamine; For health reasons. Isocyanate compounds have been used in the form of crosslinkers for polyesters, but the resulting coating formulations have lower corrosion resistance compared to the crosslinking coating formulations with phenolic crosslinkers Yo, in addition to that it is required in the manufacture of iad Ail coatings Use of isocyanate compounds for health reasons. Phenol-terminated polyesters have been linked with melamine crosslinkers, but melamine is not required for health reasons as indicated above. Polyesters are also terminated with an acid—p-hydroxybenzoic acid 01007/56102016/a-0; But

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It is also desirable in the paint filling industry to avoid hydroxybenzoic acids, as parabens are substances of high concern. Polyesters formed from the reaction product of polyols 0077015 and bis-epoxies were used reacting with phenolic carboxylic acids / esters © La acids/esters, but carboxylic phenols are also not required in the manufacture of Packaging coatings industry for hygienic reasons. The polyesters are further terminated with phenols 0060015 from carbanol; known susceptibility 560514263; But it is also an article of interest. There is a need among some consumers and brand owners in the paint packaging industry for paint formulations that are free; or substantially free of; Ve bisphenol A A and polyvinyl chloride, and where it does not suffer from the defects mentioned above. GENERAL DESCRIPTION OF THE INVENTION The present invention relates to acrylic grafted polyether free fi resins acrylic grafted bisphenol-A based on VO phenol stearic acid coating compositions having lawl ) grafted polyether cell SY Methods for coating substrates using coating formulations; and substrates coated using paint formulations. as used in this document; The expression “phenol stearic acid compound” is a pane of the reaction product of oleic acid and phenol where the initial reaction product is acid-0(-01) 0-hydroxyphenol)-octadecanoic 10—(p—hydroxyphenyl)-octadecanoic acid (also known ae 1(10)-(hydroxyphenol) octadecanoic) 9(10)—(hydroxyphenyl) coctadecanoic acid) and where (Se) the other substances formed from the reaction are oleic acid and phenol in the reaction product. In some embodiments of op AY) the difunctional hydroxyl phenyl segment Yo has the lowest used For the formation of poly fi) resins inlaid with Evie acrylic

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molecular weight greater than about ovr The lowest difunctional hydroxylphenol segment used to form acrylic-doped polyether resins does not have two or more unweakened hydroxyl groups attached to two or more of their carbon atom rings Five or six different atoms in a piece have a molecular weight of less than approx

1 00 such structures have molecular weights less than about 500 and/or have two or more unweakened hydroxyl groups bonded to two or more carbon rings

It has five or six different atoms in a piece that has a molecular weight of less than about 5000 and is therefore susceptible to internal disordering and therefore undesirable for use in coating formulations that come into contact with food or beverages. They are not monomers or dihydroxyphenol segments

P| Minimum to form poly resins functional difunctional hydroxyl phenyl segments 0 and/or not including two or more than ©0000 acrylic doped with a molecular weight greater than about unweakened hydroxyl groups bonded to two or more carbon rings It has five

or six different atoms in a piece having a molecular weight of less than about 5000 is liable to be internally disordered and therefore undesirable for use in coating formulations in contact with food or beverages.

5 In dime embodiments the acrylic grafted polyether resin ashe can be prepared by a method involving the reaction of a dihydroxyl 0000 and/or a diamine compound with a phenolic acid compound Stearic phenol stearic acid compound to produce diphenol Reaction of diphenol with

diglycidyl ether compound ji) to form polyether ji Js resin resin Y. Mixing acrylic-doped polyether resins with an ethylenically unsaturated monomer component in the presence of an initiator to form Polyether resin inlaid with acrylic. Acrylic grafted polyether resins can be crosslinked with phenolic resins to produce coating formulations. Acrylic grafted poly-Ji resins can be used to form coating compositions ld excellent flexibility; Hardness and resistance to food injuries

Yo and drinks. in some embodiments; The present invention includes methods for coating a substrate by means of

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_ Qo _ Placing the coating composition on the substrate. Coated substrates using coating formulations are also detected. in some embodiments; The substrate is overlay or packaging Detailed Description: As used in the above-discussed embodiments and other embodiments of the disclosure and 0 protections described herein;. The following expressions generally have the meanings as indicated but such meanings do not represent a limitation of the scope of the invention if the usefulness of the invention is achieved by deriving a more comprehensive meaning for the following expressions. The present invention includes substrates coated with at least Lila with the coating composition 00 of the invention and methods for coating the substrates. The term “substrate” as Ye used herein includes Se without restriction; le cle “metal cans” @easy—open—ends packing containers; containers Receptacles or any parts thereof used to carry, fit into or come into contact with any type of food or beverage.Expressions also include 'substrate', 'dalek', food containers and the like for example and not limited to “dua ends” (“can ends lal”) can be stamped from VO can end stock dle stock and used in food and beverage packaging. The present invention relates to acrylic-doped bisphenol-free polyether resins based on phenolstearic acid Coating compositions with coll SVL grafted polyether resins Methods for coating substrates with the coating compositions Coating substrates with the coating compositions In some embodiments of the invention the difunctional phenyl hydroxyl segment 0 minimum used to form polyether resins fi) grafted acrylic with a molecular weight greater than about 0600 ; the hydroxyl segment is not included in SN bi-functional looms used to form acrylic-doped polyether resins on two or more unweakened hydroxyl groups bonded to two or more 9-carbon rings (9 carbons having five or six different atoms in a segment having a molecular weight of less than about ony). Compositions with Yo molecular weights less than about 5000[ or where they contain two or more hydroxyl groups

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Undoubled hydroxyl groups bonded to two or more carbon atom rings with five or six different atoms in a segment having a molecular weight of less than about 50 800 are thus subject to internal misalignment and therefore undesirable for use in coating formulations that come into contact with food or beverages. Not be monomers or lower difunctional hydroxyl phenolic trimers to form acrylic-doped polyether© resins having a molecular weight greater than about ©0000 and/or not having two or more unweakened hydroxyl groups attached to two or more five carbon rings or six different atoms in a piece having a molecular weight of less than about 5000 is liable to be internally disordered and therefore undesirable for use in coating formulations in contact with food or beverages. in certain embodiments; Acrylic grafted polyether resins may be prepared by a method involving the reaction of a 0 dihydroxyl compound and/or a diamine 0 with a phenolstearic acid compound to produce a diphenol; Reaction of diphenol with a diglycidyl ether compound (ju) to form a poly resin (of) and mixing the polyether resin with an ethylene unsaturated monomer component in the presence of a starting material to form an acrylic grafted polyether resin. Acrylic grafted polyether resins can be used to form coating compositions for them

0 flexibility (lies) toughness and resistance to food and beverage injuries. For example, but not limited to, the 0 dihydroxyl compound can include 1 4-cyclohexane gh methanol “1,4-cyclohexane dimethanol cbutane diol neopentyl glycol (F) cneopentyl glycol cyclohexane dimethanol (1,3-cyclohexane dimethanol) ethylene glycol propylene glycol 0 propylene glycol 1 = diol ©1,3-010080 » gla ctrimethylol propane ethylene glycol Je diethylene glycol polyether glycol _benzyl alcohol -Y (benzyl alcohol 2-ethyl hexanol POLYESTER polyester polycarbonate a hydroxyl functional polyolefin or a mixture thereof; the Yo diamine compound may include a piperazine compound cethylene diamine hexamethylene diamine a fatty diamine or a mixture thereof and may include Diglycidyl ether rod

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—y—

- 1,4 of diglycidyl ethers on diglycidyl ether compound “butane diol” ¢1,4-cyclohexane dimethanol gla cyclohexane gh neopentyl glycol neopentyl glycol 1 “propylene glycol J Sida propylene ethylene glycol J Sula cdimethanol di trimethylol propane <1,3-propane diol ?-propane diol © benzyl alcohol polyether glycol “diethylene glycol” polyester “polyester” 2-ethyl hexanol ethylhexanol —Y “benzyl alcohol hydroxyl functional” polyolefin with a hydroxyl functional group “polycarbonate carbonate”

(polyolefin or a mixture thereof.

0 The compound Jp-stearic acid may be expressed in a molar ratio of about 1 : 1 of the hydroxyl group or the amine functional. It is possible to obtain a slight excess of phenolstearic acid compound; As it can lead to some ester formation when the epoxy reacts to form the polyether (polyether ji) or an excessive amount of Sut hydroxyl or cond as it can lead to a broader poly diffusion of the formed polyether.

_ 77100017615 monomers without a functional group and/or with a hydroxyl functional group optionally at a higher level than acid functional monomers can be used to put acrylic-doped polyfi resins in solution. for example, and not as a limitation; Acrylic-doped polyether resins may be prepared from an unsaturated ethylene monomer component having unsaturated ethylene monomers without a methylated functional group; For example

“methyl methacrylate (fie butyl acrylate but not exclusively; butyl acrylate 0 and the like and mixtures of benzyl methacrylate terminators such as styrene; eg functional monomers and optionally in quantities less than Functional monomers hydroxy propyl methacrylate “Sy Ste” (but not limited to; hydroxypropyl “glycidyl methacrylate” chydroxy ethyl acrylate acrylate Ja)

Yo acrylic acid methacrylic acid acetoacetoxyethyl methacrylate phosphate esters monomethacrylate and the like and mixtures thereof. in some embodiments

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A 1778 Invention; The monomer with the hydroxyl functional group is added at a level of up to about ethylenically unsaturated by weight of the unsaturated monomer component mixture The monomer with the acid functional group is added at a level of up to about ethylenically unsaturated by weight of the unsaturated monomer component mixture. in some embodiments; Approximately 7700 at the level of acetoacetoxyethyl methacrylate © acetoacetoxyethyl methacrylate by weight of the unsaturated ethylenediaminetetraacetate monomer component mixture is added. Phosphate 7700 can be added up to about (Pam-400 5 Pam-200 5100008: 800-100 (ie) esters of monomethacrylate level up to about 7780 by weight of the ethylene unsaturated monomer component mixture. In some By weight of the unsaturated monomer component mixture 750 to about 10 embodiments; it is about This acid functional group methacrylic acid with an amine to form a salt allows the acid monomer poly resin The acid monomer neutralizer equation sale is an acrylic-doped ether dispersible in water It can include for example not Jie ctertiary amine without restriction; ammonia 807010018; tertiary amine _ 7-dimethylamino-7-methyl “dimethylethanolamine exclusively dimethylethanolamine butylamine gli » 2-dimethylamino-2-methyl -1-propanol -1-propanol or a combination thereof, for example but not limited to, the neutralizer “tributylamine” may be used on the amount of acid to be neutralized in a For the .tl 70010 system in an amount of up to approx. Acrylic grafted polyether resins can be prepared in the presence of a primer. Ye starter can be added over the course of the salad) starter material after the mixture has cooled. in some embodiments; is added

Jie azo compounds jl candi compounds h. The starting material can include without " 2,2-820- azo-_bis(isobutyronitrile) = oF but not limited to JE eg 2,2 -820- (©001011/ir5)150a5; 7 »'- 531 - Bis( ; -dimethylvaleronitrile) 1-t-butyl-butyl-azocyanocyclohexane)-1H 5(bis(2,4-dimethylvaleronitrile) yo e.g. hydroperoxides (©01006*810/A820©0/8000; hydroperoxides and cumene hydroperoxide t-butyl hydroperoxide but not limited to; +- butyl hydroperoxide

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ccumene hydroperoxide peroxides such as but not limited to benzoyl peroxide ccaprylyl peroxide di-t-butyl peroxide di-t-butyl peroxide =F oF Di (1- butylperoxy) butyrate ‎="Y oY Jay) cethyl 3,3'-di(t-butylperoxy) butyrate (©- dady) Jad —t ethyl 3,3'-di (t-amylperoxy) butyrate © peroxy-?-ethylhexanoate t= 10 camylperoxy-2-ethyl hexanoate )0 7 7-tetramethylbutyl-peroxy “Y=Ji)hexanoate 1, 1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoate » and]- butyl peroxybutylate; —t 5 “t-butyl perphthalate t-butyl perbenzoate plus Jie cpercarbonates to name but not limited to di-1(cyano-1-methyl) ) peroxydicarbonate-1)01 “cyano-1-methylethyl)peroxy dicarbonate perphosphate —t “perphosphates butyl per oke t-butyl peroctoate and the like, and mixtures thereof. in some embodiments; The starting material is present in an amount from about 01 to about 715 and alternatively from about 1 to Vo about Jo depending on the weight of the monomer mixture. It is a preferred starting material to achieve a carbon-preference It is benzoyl peroxide No. 56020. It is also possible to pre-form the acrylic polymer and then add it to the polyether epoxide and react the functionalized acrylic acid with the epoxide and then disperse the sale ester grafted material with water. 0 in some embodiments; Acrylic grafted polyether resins are crosslinked with a phenolic crosslinker to form a curable coating .composition The weight ratio of phenolic crosslinker to acrylic grafted polyether resins can be from about 45/5 to about 10 /50 at about 7710-71 solids. The crosslinking coating formulation can provide excellent wafer efficiency at very short roasting for yo-file applications. laa The mixing of mul 980860 acrylic polyether resin and crosslinker can occur in the presence of a cure catalyst.

“yam, for example but not limited to Cure catalysts. Solidification catalysts include M-tolenesulfonic acid —p © 0006; benzene sulfonic acid, dodecylbenzene sulfonic acid, and the like, and mixtures thereof, phosphoric phosphoric acid toluene sulfonic acid other in the coating composition” as polymers In some embodiments the polymers may be mixed with polyesters; polycarbonates and not exclusively poly(ethers) JBN ©

Js “polycarbonates, polyurethanes, and the like; In addition to mixtures thereof. Coating compositions for tamper coatings are in some embodiments about © to about 10 seconds at about 4060 degrees Fahrenheit to about 100 degrees Fahrenheit; Alternatively about © seconds to about 10 seconds at about ½ degrees Fahrenheit to about 10000 degrees Fahrenheit.

Se 0 that the acrylic grafted polyether resins and coating compositions of the invention comprise conventional additives known to those skilled in the art; for example, and not as a limitation; flow agents Luin agents surface active agents defoamers anti-crater additives canti—cratering additives lubricants lubricants thermosetting additives 621-12616356 and catalysts sclerosis cure

.catalysts 0 in some embodiments of the invention; One or more acrylic grafted polyether resins eg Jie or acrylic grafted polyether resin coating compositions are applied to a substrate; easy open ends; packing containers; containers; bags; The limbs of le (Ql ean) and not, or any parts thereof, used to hold or come into contact with any type of food or beverage. in some cla

0 avatars; One or more coatings are applied in addition to the coating compositions of the present invention; For example, but not limited to, a prime coat can be placed between the substrate and the paint composition. Coating compositions may be applied to substrates in any manner known to those skilled in the art. in some embodiments; The coating formulations are sprayed or roller coated as a substrate.

7718 when placing; Coating formulations contain; for example, and not as a limitation; Between about Yo of about 77680 to about polymeric solids by weight Polymeric solids of about 7400 and about

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-11- A solvent. For some applications; typically those other than spraying; Solutions of 0 can contain, for example, but not limited to solvent-borne polymeric solutions and about 77680 by weight polymeric solids. Organic solvents are used in 771 in about some embodiments to aid roller coating or other application methods and these solvents may include 2-butoxy—V— butoxy-ethanol 7-n-butanol butanol -© awd on me; without ©

Cal gush Butyl —N 6007/1606 glycol Propylene glycol xylene 1-A610800; xylene diethylene glycol monoethyl ji di(ethylene glycol monoethyl) “N-butyl cellosolve” and mixtures of other ester solvents and ester aromatic solvents and aromatic solvents ©1161 thereof. In some embodiments; COMPOSITION WITH PROPYLENE GLYCOL The resulting coating compositions are applied in some embodiments by the conventional propylene glycol 0 methods known in the coating industry.Thus, but not limited to, spray, roller, dip, file coating and coating application methods can be used to name a few. by flow.in some embodiments;after

Yoo Stilt; The coating composition thermally hardens at temperatures in the range of about sufficient to effect hardening sAD °C; Alternatively higher You to about fully fugitive components plus vaporization of any fugitive components Ye The coating compositions of the present invention may be tinted and/or opaque using known pigments in some embodiments. For many uses Opacifiers and Opacifiers 5 including but not limited to food use Dye can be titanium SB or carbon black zinc oxide The resulting coating compositions are applied in some embodiments by conventional methods Ye dioxide thus; For example, but not limited to, the coating industry, which is known in the coating industry

Ash) films can be used to spray with a reel; dipping And methods of applying the coating flow for both chips and dyed. in some embodiments; after placement on a substrate; The coating composition thermally solidifies at °C; You are approximately 11°C to about 11°C in the range of about an alternative higher long enough to effect complete solidification as well as vaporize any volatile ingredients. Yo 561761896 containers da beverage containers are placed for for the substrates specified on

Yo A015 to about #0 in some embodiments at a rate in the range of about coating A

-117-

Milligrams per square inch of polymer coating per square inch of exposed substrate surface

Substrate surface 505©0»©. in some embodiments; Water dispersible paint is applied

with a thickness between about 1015 oY A and about 01 msi

For substrates specified as beverage easy-open—

© 6005; The coating is applied in some embodiments at a rate in the range of about Ao to about Yo

Milligrams per square inch of polymer coating per square inch of surface

5S) exposed. Conventional fill coating formulations are applied to metal at approximately 777 to approx

VEY Celsius. Some of the coating formulations of the present invention achieve good results when

about 771 °C or less; Jie at about 701 degrees Celsius or less. The low 0 temperature dap provides an energy saving to the coating tool; It can allow the use of different alloys; Jie

Tin-plated steel used for easy opening ends. That is also allowed

By recirculating the ends together with the body 680. When used as a tip coating

Jew opening with a metal container showing the coatings of the invention

Resistant to distilled beverages Lise retorted beverages Acidified coffee Vo coffees Isotonic drinks 15010016 and the like. in some embodiments;

The solids content of the coating formulation is greater than about 778 and the coating formulation has a viscosity of

Dilute Yo to about 100cP at 770 solids or higher to produce a wafer weight

About + to about MST A (milligrams per square inch) so that epidermal blister is reduced

so that the wafer can have good chemical resistance; Jie aluminum pick resistance (Se Yo) Some of the coating formulations of the present invention were used for both tip applications

Easy to open internally and externally.

Examples

The invention will also be described with reference to the following non-exhaustive examples. must be from

It is understood that variations and modifications may be made to such examples by those skilled in the art Yo without departing from the content and scope of the invention.

Example 1 - Synthesis of diphenol

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— \ —

YA grams of 1;4-cyclohexane dimethanol “1,4-cyclohexane dimethanol” is heated

7 grams of phenol stearic acid A00800 and 10 grams of butyl acid

Stanwyck butyl 5180016 acid using a distillation column and height to

YYO is a recurring degree. Approximately VA g of water was produced. Xylene was used as a substance

© carrier solvent to achieve an ax final acid less than © mg [KOH]

resin aha

1 Ja - Synthesis of acrylic-doped polyether resin

pha 195 of diphenol is heated from example 0094 grams of dicyclohexane dimethanol

cyclohexane dimethanol diglycidyl ether ji) and 0.1 gram of “0”-phenol to 2-phenyl imidazole to YA grade Adie and kept for 1 hour. The weight was

Epoxy 6007 EY 7 equivalent. The mixture was kept for an additional 1 hour at 098 degrees Aggie

The epoxy equivalent weight was FAY

Ja ¥ - Synthesis of acrylic-doped polyether resin

Ve gram of acrylic grafted polyether resin from Example 1 and 1000 g of Vo butyl cellosolve were heated to 100°C. to the resulting mixture; has been added

butyl butyl acrylate aha 01 methacrylic acid methacrylic acid ala VA

benzoyl peroxide pha © sstyrene 1 gram of styrene £Y acrylate

throughout? 1 hour under a nitrogen cover blanket 01009860. The mixture was kept for Vo

min 1 gram of +- t-butyl peroctoate was added and the mixture TY sad YS min was kept. Another quantity of 1 gram of +- butyl per octate was added and the mixture was kept for a period of time

0 minutes. The resulting mixture was cooled to 860 °C. phaVO of dimethyl has been added

diemethylethanolamine in 10 grams of water; This is followed by an extra YA gram

From Alma Saath Al-Shear. Then z is an independent scattering 0” that is translucent.

example; - Synthesis of coating composition

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— \ ¢ —

YA added grams of phenolic resin dissolved in YA grams of butyl

cellosolve to 100 gm of JB ? acrylic grafted polyether resins. been withdrawn

Coating film chips obtained on ETP steel with a #7 "bar and roasting for 10 minutes.

at Yoo degrees Celsius. An amber wafer (ala) has been produced which has a solid GH QB

0 be able to withstand MEK 001 rubbing with little deformation dan and have 7001 cut adhesion across the tape

without cracking after 010 psi reverse impact; And without blush or loss of adhesion after 1 hour in

boiling water.

Example © - gla Galas Phenol

79.9 grams of 1 ;- cyclohexane gla methanol l,4-cyclohexane “0 £0 dimethanol” gram of phenol stearic acid and 10 gram of

butyl stanoic acid 51380016 acid under nitrogen to YYo residual degree over

1 hour in a 1 liter stirrer flask” thermocouple temperature controller

thermocouple temperature controller and a Vigreux das 01 (01 tipped lize) distillation column

; inch of fill glass tube strip). The mixture was kept until the temperature of the column head dropped to a Vo of about 1 °C. The column has been converted to Dean Stark's barrier and xylene has been added to obtain

On return ready within 1 hour. The mixture was cooled and the final acid number was; mg [KOH g

resin.

Ja > - Synthesis of acrylic-doped polyether resin

Aha 148 of the diphenol from example # is heated; 40.4g of CVC ( YY-GE (Industries) 1 Diglycidyl Jul of +1 ¢—Diglycidyl Cyclohexane Jl 03+g of

- Phenol imidazole except 2-0060 to 1175 degrees Celsius and preservation for hours.

The epoxy equivalent weight was 1 4 0 7 and the viscosity was IN 7 Poises at an Oe.

Example 1 - Synthesis of gla phenol

451 grams of phenolstearic acid, 47.1 grams of piperazine, and 8100 grams of yo butylstanoic acid were heated under nitrogen to yyo at yep over 1 hour in a beaker. 1 liter

‎Evie

ag \ — equipped with a “stirrer thermocouple temperature controller” and a packed distillation column (ag 0 Vigreux) with a tip; inch of Lad glass tube section Lis. The mixture was cooled until the temperature of the column head dropped to about Te °C. The column was shifted to a Dean Stark buffer and xylene was added to obtain a ready-return for 7 h. The mixture o was cooled and the final acid number was 4 mg <00 g resin. Example A - Diamide synthesis then heating 17591 017 phenolstearic acid; 175 g Dytec A + 15, gram of YA butyl 5180016 deionized acid in a glass flask The reaction temperature was controlled such that the head temperature on a distillation column does not exceed about WA °C as the batch temperature is raised to YYO °C C. The batch was held at about YYo dap C until the head temperature fell below about 71 C. Water continued to distill (approximately Av g) to a maximum for two hours; then converted to The azeotropic xylene © 2. Approximately 01 g of xylene remains in the di ad ©0180710. The mixture has been treated to an acid number of about © mg KOH/g of resin and a basic number of less than Vo eg. 4 - Diester synthesis d ester AT) gram phenolstearic acid” 060 gram cyclohexane dimethanol ,5 gram butylstanoic acid was heated to 1885°C in a glass flask. The reaction temperature was controlled so that the temperature of the head on a distillation column did not exceed about aA degrees YEP as the batch temperature rose to 71 degrees YEP. Then hold 0 the batch at about 775 degrees Celsius until the temperature of the head falls below about 71 degrees Celsius. The water continues to distill (approximately Av g) for up to sad 2 hours; Then convert it into azeotropic xylene. There is about 1 0 gram of xylene left in the diester. The mixture was treated to an acid number of about ¾ mg / 100 g of resin. Example 01 - Epoxy Upgrade

800 grams of diamide from example 807179 grams of cyclohexane dimethanol diglycidyl ether and ? grams of = 2-phenyl imidazole to 175 °C in a glass flask. There is little heat expulsion to 185-1858°C. The sad mixture was kept for four hours until the viscosity reached Ve) p 101-6420 5 °C viscometer with cone and plate 01816). The mixture was cooled to 171°C and Vor gram of butyl cellosolve and 1501 gram of butanol A501800 were added. The mixture was cooled and poured at room temperature. Example 11 - Upgrading the epoxy Yo and then heating 07907 grams of diamide from example 1e a gram of butane diol diglycidyl ether (ji) and ? grams of “-phenol imidazole” to 1175 °C in a glass flask. There is a slight exothermic to 185-1786 °C. The mixture is kept for four hours until the viscosity reaches Yeo (Pp YY v= Ae ° YEP viscometer with cone and plate). Room Temperature Example 11 - Emulsion Synthesis (epoxy-acrylic grafted emulsion) 900g of the epoxy in Example 01 was heated to dan 111°C in a glass reactor 01855. 40g was added of butylcellosulf 5 μg of butanol The following mixture was then added over the course of 2 hours: aha VOY of methyl acrylic acid 670 “methyl 80/168610 0 g of styrene VY” gram of ethyl acrylate ethyl (sha©) acrylate of benzoyl peroxide and 17 g of butylcellosulq. After feeding the contents of the reactor were kept at 00 V°C for another hour. A g was added From Beer Octat peroctoate and the sad mixture was kept for another hour. The mixture was cooled to 910 °C and a mixture of 006 g of dimethyl yo dimethylethanolamine and 10 g of water was added to the reactor on Vo Jae

for \ —

minute. The temperature was kept at AC degrees Celsius for Te min. 1714 grams of

water and the mixture was cooled.

11 Ja) - Synthesis of an acrylic-doped epoxy emulsion

Then heat 7001 grams of epoxy in Example 01 to 11 degrees YEP in a glass reactor.

2 1 gram of butylsilosulfq and 1 gram of 0.0 butanol were added thereafter; has been added

The following mixture over the course of 2 hours: Av gram of methyl acid LST 94 grams of styrene; 1

grams of ethyl acrylate; pba TY of benzoyl peroxide and 37g of butylcellulosulf. after

feeding ends; The contents of the reactor were kept at 155 °C for another hour. A added

grams of per octate and the mixture was kept for another hour. The mixture was cooled to 900 °C day 0 and a mixture of 506 g of dimethylethanolamine and 57 g of water was added to the reactor

Over the course of yo minutes. Then keep the temperature at YEP degree blood for 1 minute. Then there is an addition

AYA grams of water and the mixture was cooled.

16 Ja) - Synthesis of an acrylic-doped epoxy emulsion

The 00,760 grams of epoxy in Example 11 is heated to 111 degrees Celsius in a glass reactor. Yo added Ye grams of butyl cellosulfate You grams of butanol 0. Thereafter; has been added

The following mixture over 2 hours: VEE 1 gram of methylacrylic acid; 175 grams of styrene;

VY 1 gram of YA cethyl acrylate 1 gram of benzoyl peroxide and 11 grams of

Butylcellosolq. after the end of feeding; The contents of the reactor were kept at 155 aggie degrees for a period of time

another hour. 1 gram of per octate was added and the sad mixture was kept for another hour. 0 _ mixture was cooled to 90 Baie degrees and a mixture of 0101 grams of dimethylethanolamine was added

dimethylethanolamine and 1,011 grams of water into the reactor over a period of 15 minutes. saved

The temperature at AO is degressive for a period of Ve min. 711 005 grams of water was added and cooled

the mixture.

Example 11 - Upgrading the epoxy

Fad

-1 pm

Ave gram of diester of JB heated 507979 gram of dimethanol dicyclohexane

cyclohexane dimethanol diglycidyl ether and ? grams of = phenol

imidazole to 175 °C in a glass flask. There is little heat exothermic to Aap 185-1758

percentage. The mixture was kept for four hours until the viscosity reached 101-818 (8 001) °C.

© Cone and plate viscometer). The mixture was cooled to 071 degrees Aggie and You grams were added

of butylsilosulfq and 1501 aha of butanol. The mixture has been completely cooled and poured at 0°C

room temperature.

Example 176 - Synthesis of an acrylic-doped epoxy emulsion

760,000 grams of epoxy in Example 11 is heated to 111 degrees Celsius in a glass reactor. 01g of butylcellosulf and 1051g of butanol added. after that; has been added

Next mixture on Jae 2 hours: VEE 1g of methylacrylic acid 175g of styrene

‎VY styrene ‎grams of ethyl acrylate; 79 grams of benzoyl peroxide and 1 gram of butyl

cellosolve. after the end of feeding; The contents of the reactor were heated at 155 °C sad hours

other. 17 aha peroctoate was added and the mixture was kept for another hour. Vo the mixture was cooled to 900°C and a mixture of 101g dimethylethanolamine was added

and 110 grams of water into the reactor over the course of 15 minutes. The temperature was kept at AS degrees

Stomach for Ve minutes. aha 01971 water was added and the mixture was cooled.

Example 01: creating a mixture composition

zon 00 (a percentage of phenyl stearate diamide - Yo epoxy grafting) was crosslinked to an acrylic graft (cyclohexane dimethanol diglycidyl ether)

Epoxy diamide cyclohexane dimethanol diglycidyl ether epoxy diamide from

Example VY with hydroxyalkamide (Primid 201-552) hydroxyalkamide at Zo wt.

The admixture formulation has excellent corrosion resistance after 90 minutes suction at YOu °F

Solution 1 7 of Brian. Marginal flushing of the blend is after 90 min suction at YOu °F YO in a 711 lactic acid solution compared to a bisphenol epoxy coating

commercial bisphenol A coating A. Overall efficiency is improved.

a

— \q —

‎:18 JE Synthesis Composition Mix

70:70 (ratio of phenolstearate diamide - epoxy graft to acrylic graft) of

Cyclohexane Dimethanol Diglycidyl Ether Epoxy Diamide of 11 JB with Emulsifier

phenyl methyl silicone emulsion at 4 7 by weight. have to formulate

0 mixture Excellent corrosion resistance after 00 min suction at YOu °F in a 7 1 solution of

Brian. Rose is better than AY JED

Example 09: creating a mixture composition

70:70 (ratio of phenolstearate diamide-epoxy graft to acrylic graft) of

butane diol diglycidyl ether epoxy au diamide 0 of example VE with a phenolmethylsilicone emulsion at; 7 wt. have to formulate

The mixture has excellent jet resistance and fluorescence resistance.

‎:01 JE Mix composition synthesis

70:70 (ratio of phenolstearate diamide - epoxy graft to acrylic graft) of

butane diol diglycidyl ether epoxy au diamide | 0 from Example 11 with a phenyl methyl silicone emulsion

emulsion at 4 7 wt. The mixture formula has poor corrosion resistance and fluorescence resistance.

a

Claims (1)

1. Protection elements where the acrylic grafted polyether resin piece has a minimum Gentar-1 difunctional hydroxyl phenyl segment acrylic grafted polyether resin used to form acrylic grafted polyether resins molecular weight greater than about 5080; Whereas the difunctional hydroxyl phenyl segment © used to form the difunctional hydroxyl phenyl segment does not include two or more unweakened acrylic grafted polyether resin groups bonded to two or more carbon rings. hydroxyl groups Hydroxyl has five or six different atoms in a piece that has a molecular weight less than about carbon atom rings Oa ye according to the element acrylic grafted polyether resin fi) "- acrylic grafted resins where Polyether resins dotted with acrylic 0 protection are prepared by a method that includes polyether resin diamine or a dihydroxyl compound a) Reaction of a dihydroxyl compound to produce a phenol stearic acid compound with a phenol stearic acid compound 000000000 |1008 tdiphenol diglycidyl ether ji) with diphenol compound diphenol phenol Gall b) and tpolyether resin react to form polyether resin 0 monomer unsaturated ethylene Se xe polyether resin ether (Jal mu) c) mixing initiator in the presence of matter prefix ethylenically unsaturated monomer component 00 acrylic grafted polyether resin . ji) to form poly resins according to the element of acrylic grafted polyether resin fi) poly Slav phenol stearic acid compound where the compound includes Phenolstearic acid oF protection a — \ \ — on -0(-01-hydroxyphenol)-10-octadecanoic acid ~(p—hydroxyphenyl)— -octadecanoic acid; Coating © .coating composition acrylic grafted polyether resin pursuant to claim 7 wherein the reaction mixture comprises a crosslinker 7" 1-grafted poly-fi resin In acrylic acrylic grafted polyether resin according to Clause 1 dua The crosslinker comprises a phenolic resin phenolic resin 1-fi grafted with acrylic grafted polyether resin according to Clause 1 protection oF where the dihydroxyl compound comprises 1; ¢— cyclohexane gla methanol ¢ 1,4-cyclohexane dimethanol butane diol neopentyl cneopentyl glycol J Sula ) ¢ 7 - 1,3-cyclohexane-dimethanol—-cyclohexane cdimethanol (ethylene glycol J Sula propylene glycol 1 “propylene glycol *- B propane diol <1,3-propane diol trimethylol propane di 0 diethylene glycol polyether glycol benzyl alcohol —Y benzyl alcohol 2-ethyl hexanol hexanol; Poly (polyester ji.) polycarbonate “polycarbonate” polyolefin with a hydroxyl functional group (polyolefin or a mixture thereof. Yo + polyether resin ju} according to the oF claim where it includes Diamine compound on piperazine compound Ethylene diamine A _— \ \ _ cethylene diamine hexamethylene diamine chexamethylene diamine fatty diamine (fatty diamine or a mixture thereof. 4-polyether resin ji) sll according to claim 7 where the diamine compound comprises ©glycidyl diglycidyl ether compound ji) contains diglycidyl ether ji from; 4-cyclohexane dimethanol “4-cyclohexane dimethanol butane cdiol neopentyl glycol glycol El0800©01; cyclohexane cyclohexane cdimethanol (ethylene glycol J Sula propylene glycol *- propane diol <1,3-propane diol trimethylol propane di 0 For ethylene glycol “diethylene glycol” polyether glycol or a mixture thereof. polyether resin Less than about 10 mg [KOH resin Vo 11-fi poly resin] acrylic grafted polyether resin according to protection element dua) resins are prepared acrylic grafted polyether resin in the presence of catalyst 0 11-fi acrylic grafted polyether resin according to Claim 01 where the catalyst is It is an acid catalyst. enol stearic acid compound in YO molar ratio of about 1:1 of the hydroxyl group or amine function EVE — \ Ad — 40-fi acrylic grafted polyether resin of claim 1; wherein polyetherresin ji is prepared in the presence of an initiator comprising [- butyl peroxybenzoate —t «t-butyl peroxy benzoate Dibenzoyl peroxide 0 0 “dibenzoyl peroxide ?; ?- tetramethyl butyl-peroxy-?- Ji) hexanoate -/R2610:4-2610:4-analog 1,1,3,3-161:8008 cethylhexanoate or a mixture thereof. 1- A coating composition that includes poly (fy) resin grafted with acrylic 1. According to the protection element acrylic grafted polyether Magu 0 according to the coating composition includes laying the substrate - a method for coating substrate 1 to substrate 11 of the coating composition A The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa