CN1186803A

CN1186803A - Novel bis (mono-and diperoxyoxalates) derived from dihydroperoxides and alkyl and alkylperoxy halooxalates

Info

Publication number: CN1186803A
Application number: CN97126234A
Authority: CN
Inventors: J·桑切斯
Original assignee: Elf Atochem North America Inc
Current assignee: Arkema Inc
Priority date: 1996-12-30
Filing date: 1997-12-30
Publication date: 1998-07-08

Abstract

A novel bis(mono- or diperoxyoxalate) composition of Structure A, A and use of the novel bis(mono- or diperoxyoxalate) composition as an initiators for curing of unsaturated polyester resins and for polymerizing ethylenically unsaturated monomers are disclosed.

Description

Novel two (one-and two-cross barkites) derived from dihydro-peroxidase and halo oxalic acid alkyl ester and halo oxalic acid alkyl peroxy ester

The right of priority that the application requires is the provisional application S/N 60/034,528 of 30 applications December in 1996.

The present invention relates in chemical field, to be divided into the material of novel two (-and two-cross barkites) of structural formula category-A,

(Q, Q ¹, R ¹, R ², R ³, R ⁴And R ⁵Be defined in the brief summary of the invention part provide) it can be by in the presence of organic bases or mineral alkali, dihydro-peroxidase is (as 2,5-dimethyl-2,5-two hydroperoxy hexanes and 2,5-dimethyl-2,5-two hydroperoxies-3-hexin) prepare with the reaction of halo oxalic acid alkyl ester and alkyl peroxy oxalyl halogen (as chloro ethyl oxalate and t-butylperoxy oxalyl chloride); Also relate to Preparation Method And The Use.The barkite of crossing of structural formula A has the intrinsic application performance, makes them can be used as synthetic intermediate, be used as the initiator of polymerization ethylenically unsaturated monomer and be used to solidify the unsaturated polyester resin composition.

In the polymkeric substance industry, need the effective radical initiator of polymerization ethylenically unsaturated monomer under the lesser temps, so that obtain to have more high tensile performance and polymkeric substance other mechanical propertys, that molecular weight is higher and/or improve the speed of polyreaction, thereby reduce cost so that produce existing polymkeric substance with production rate faster.Under latter event, more effective radical initiator can make polymer producers improve throughput and needn't build new and expensive production equipment.Also need a kind of radical initiator in the polyester industry, it can quickly and/or more solidify unsaturated polyester resin under the low temperature.Novel two (one-and two-cross barkites) compound of structural formula A of the present invention can satisfy these needs in the polymkeric substance industry.

People such as P.D.Bartlett (J.Am.Chem.Soc., 82,1762-8,1960) have described two and have crossed the decomposition kinetics of oxalic acid two-tert-butyl esters (CAS RN1876-22-2) in solution, and find that its transformation period 60 ℃ time the in benzene is 6.8 minutes.(J.Am.Chem.Soc. in the article of P.D.Bartlett and R.E.Pincock subsequently, 82,1769-73,1960), disclose two and crossed the oxalic acid di tert butyl carbonate and several OO-tertiary butyls O-alkyl one is crossed the barkite decomposition kinetics of (comprising that OO-tertiary butyl O-ethyl one is crossed barkite and OO-tertiary butyl O-benzyl one is crossed barkite).Based on the data that provide in the document, 10 hours half life temperature (temperature when promptly 50% superoxide decomposed in 10 hours) be respectively 26 ℃, 39 ℃ and 41 ℃ for the above-mentioned barkite of crossing as calculated.Therefore, two 10 hours half life temperatures crossing oxalic acid two tertiary alkyl esters are about 25 ℃, and 10 hours half life temperatures that OO-tertiary alkyl O-alkyl one is crossed barkite are about 40 ℃.Two (one crosses barkite) of the present invention, promptly 2,5-dimethyl-2,5-two (isobornyl oxygen base carbonyl carbonyl peroxy) hexane (1-4),

Found that its 10 hours half life temperatures in trieline are 20 ℃.Therefore, to cross barkite than the OO-tertiary alkyl O-alkyl in the prior art one obviously higher for the activity of novelty of the present invention two (-and two-cross barkites).

R.A.Sheldon and J.K.Kochi (J.Org.Chem., 35,1223-6,1970) have reported the decomposition rate of two mistake oxalic acid, the two-tertiary alkyl ester of various following array structures:

(R is methyl, ethyl, sec.-propyl and benzyl in the formula) these data are consistent with the data of Bartlett.

W.Adams and J.Sanabia (J.Am.Chem.Soc., 99,2735-9,1977) have described, in the presence of pyridine, with oxalyl chloride and 2,5-dimethyl-2,5-two hydroperoxy hexane synthesis of cyclic two are crossed oxalate compound, 7,7,10,10-tetramethyl--1,2,5,6-four oxa-s-3,4-dioxy cyclodecane

According to the data that provided in the document, 10 hours half life temperatures that calculate these ring-type two mistake oxalate compounds are about 80 ℃.The superoxide that it should be noted that Adam and Sanabia is that cyclic two is crossed barkite, rather than two (one crosses barkite).

People such as P.G.Griffiths [J.Macromol.Sci., Chem., A17 (1), 45-50,1982] disclose with two and have crossed the polyreaction that oxalic acid two-tert-butyl ester carries out alkyl methacrylate.

(on April 21st, 82, ICI Australia Ltd.) disclose and have a kind ofly crossed oxalic acid two-tert-butyl ester as initiator polymerizing vinyl chloride (VCl) monomer methods with two european patent application No.EP0049966.

People such as M.Schulz (J.Prakt.Chem., 324 (4), 589-95,1982) have described the synthetic and pyrolysis situation of azo two (the isobutyl-tertiary butyl is crossed barkite),

This compound is a kind of azo-superoxide of continuous decomposition.

European patent application No.EP0095860A2 (on December 7th, 83, ICI Australia Ltd.) disclose an a kind of mistake oxalate diester with following formula and have been used as initiator polymerization VCl monomer methods,

In the formula, R ¹Be the benzyl of secondary alkyl or tertiary alkyl or benzyl or replacement, and R ²It is the benzyl of secondary alkyl or tertiary alkyl or benzyl or replacement.The chloro oxalic acid tertiary alkyl peroxy esters of following formula is also disclosed in this patent application

These intermediates can be used for preparing one and cross oxalate diester.

United States Patent (USP) 4,859,794 (on August 22nd, 89, Berol Nobel Nacka AB) disclose the following mistake dialkyl oxalate of structure,

(in the formula, R=C _4-10Tertiary alkyl, R ₁=C _18-28Primary alkyl) for example, OO-tertiary butyl O-docosyl one is crossed barkite, and they can be used for causing vinylchlorid and other monomeric polyreactions.

Japanese patent application JP63/248806 (on October 17th, 88, NOFCO) and JP63/254110 (on October 20th, 88 NOFCO) disclosed the following OO-tertiary alkyl O-alkyl of structure one and has crossed barkite,

[in the formula, R ₁=H, alkyl, and R ₂=C _1-7Alkyl, (replacement) C ₆H ₅Deng]

They are as the initiator of producing smell and light vinyl chloride-base polymer.

European patent specification No.0500624B1 (on July 12nd, 94, Akzo Nobel N.V.) discloses the following allyl group superoxide chain-transfer agent of a kind of structure,

In the formula, n is the integer of 1-4, R ₁And R ₂Can be selected from hydrogen or low alkyl group, R identical or different and separately ₃Be selected from the alkyl of 4-8 carbon atom, the alkenyl of a 5-18 carbon atom etc., X can improve the reactive activating group of alkene degree of unsaturation to the free radical addition reaction, and m is 0 or 1, and Z is selected from following structure:

If Z is back a kind of structure, the compound of European patent specification No.0500624B1 is exactly a mistake oxalate compound so.Yet the material of 0500624B1 does not disclose material of the present invention, because the superoxide of structural formula A is not the allyl group superoxide, and the present invention does not cover the material of 0500624B1 yet.It should be noted that at the 5th, 7 and 8 page the superoxide inventory of 0500624B1 and in preparation embodiment and do not comprise that all one crosses oxalate compound.

Generally speaking, above-mentioned prior art two (one-and two-cross barkites) compound of structural formula A openly all.

United States Patent (USP) 3,117,166 (on January 7th, 64, authorize Wallace﹠amp; Tiernan) disclose 2; 5-dimethyl-2; the diperoxy ester derivative of 5-two hydroperoxy hexanes; as 2,5-dimethyl-2,5-two (ethanoyl peroxy) hexane, 2; 5-dimethyl 2; 5-two (2-carboxylbenzoyl peroxy) hexane and 2,5-dimethyl-2,5-two (ethoxy carbonyl peroxy) hexane.

United States Patent (USP) 3,297,738 (on January 10th, 67, authorize Wallace﹠amp; Tiernan) disclose derived from contain-C ≡ C-and-dihydro-peroxidase of C ≡ C-C ≡ C-part and the acetylene series of carbonochloridic acid alkyl ester two (peroxocarbonate), as 2,5-dimethyl-2,5-two (ethoxy carbonyl peroxy)-3-hexin, 3,6-dimethyl-3,6-two (ethoxy carbonyl peroxy)-4-octyne and 2,7-dimethyl-2,7-two (ethoxy carbonyl peroxy)-3, the hot diine of 5-.

United States Patent (USP) 3,264,274 (on August 2nd, 66, authorizing Witco Chemical Corporation) disclose the diperoxy ester of following formula,

N is 1-5 in the formula, R ₁, R ₂, R ₃, and R ₄Be selected from the alkyl of a hydrogen and 1-5 carbon atom, and R ₅And R ₆Be 3-20 carbon atom at alpha-position the ramose alkyl is arranged.

United States Patent (USP) 3,574,696 (on April 13rd, 71, authorizing Witco Chemical Corporation) disclose the acetylene series diperoxy ester of following formula,

P is 1-7 in the formula, and m and n are 0 or 1, R ₁, R ₂, R ₃, and R ₄Be selected from the low alkyl group of 1-5 carbon atom, and R ₅And R ₆Be the alkyl of 1-12 carbon atom, supplementary condition are R ₅And R ₆Be primary alkyl or secondary alkyl.M and n and be at least 1.

United States Patent (USP) 3,624,123 (on November 30th, 71, authorizing Witco Chemical Corporation) disclose two (the new peroxy esters) of following formula,

L, m, n, o and p are 0-5 in the formula, and supplementary condition are that l, m, n, o and p sum are at least 1; R ₁And R ₂Be alkyl, the phenyl of 1-7 carbon atom, perhaps R ₁And R ₂The carbon atom that is connected with them the formation cyclohexane ring that connects together; R ₃, R ₄And R ₅Be the alkyl of 1-8 carbon atom, supplementary condition are R ₃, R ₄And R ₅More than the middle none is methyl; And R ₁', R ₂', R ₃', R ₄' and R ₅' respectively with above-mentioned R ₁, R ₂, R ₃, R ₄And R ₅Identical.

According to the structure of diperoxy ester in the prior art, can't predict novel two (-and two-cross barkites) of structural formula A.

Definition

10 hours half life temperatures of organo-peroxide are defined as, and the temperature of decomposition takes place half (50%) superoxide in 10 hours.

Uncle-cycloalkyl refers to the monoradical structure:

In the formula, t is 0-2, R ^xIt is the low alkyl group of 1-4 carbon atom; Uncle's alkynyl is the monoradical structure:

R in the formula ^yIt is the low alkyl group of a hydrogen or 1-4 carbon atom; Uncle's aralkyl is the monoradical structure:

R in the formula ^zCan with R ^xIdentical or different, low alkyl group, the Ar that is 1-4 carbon atom is the aryl of 6-10 carbon atom.

As any generalized functional group or index such as R, R ¹, R ², x, n etc. occur in a general formula when once above, its each implication is separate.

Aspect material, the invention provides two (-or two-cross barkites) of a kind of structural formula A:

R in the formula ¹, R ², R ³And R ⁴Can be identical or different, they are alkyl of 1-4 carbon atom, are preferably the alkyl of 1-2 carbon atom, more preferably are methyl,

R ⁵Be the divalent group that is selected from down group :-(CH ₂) _n-(n is 1-6 in the formula) ,-C ≡ C-,-C ≡ C-C ≡ C-, 1,4-phenylene, replacement or unsubstituted 1,3-phenylene, its substituting group are following structure:

R preferably ⁵Be to be selected from-(CH ₂) _n-(n is 1-2 in the formula) and-divalent group of C ≡ C-, more preferably R ⁵Be-(CH ₂) ₂-,

Q and Q ¹Be selected from down independently of one another group: chlorine, bromine, R-O and R ⁶-OO, wherein R is selected from down group: H; 1-24 carbon atom replaces or unsubstituted alkyl, and its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, fluorine, chlorine, bromine, carboxyl and the cyano group of a 6-10 carbon atom; 3-12 carbon atom replaces or unsubstituted alkenyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-10 carbon atom replaces or unsubstituted aryl, and its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, chlorine, bromine and the cyano group of a 6-10 carbon atom; 7-13 carbon atom replaces or unsubstituted aralkyl, and its substituting group is the alkyl of one or more 1-6 carbon atom; 5-12 carbon atom replaces or the last cycloalkyl that replaces, and on naphthenic ring one or more oxygen or nitrogen-atoms can be arranged randomly, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-14 carbon atom replaces or unsubstituted bicyclic alkyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; The replacement of 7-16 carbon atom or unsubstituted tricyclic alkyl, its substituting group are the low alkyl group of one or more 1-4 carbon atom, and in addition, R-can also be structure (a),

In the formula, R ¹⁰Be the unsubstituted divalent alkyl of 1-3 carbon atom or the replacement divalent alkyl of 1-3 carbon atom (its substituting group is the low alkyl group of one or more 1-4 carbon atom), R ⁷And R ⁸Be the alkyl of 1-4 carbon atom, R ⁹Be selected from: unsubstituted 4-12 carbon atom tertiary alkyl; 4-12 the carbon atom tertiary alkyl that replaces; uncle's cycloalkyl of 6-13 carbon atom; uncle's alkynyl of 5-9 carbon atom; uncle's aralkyl of 9-13 carbon atom; unsubstituted 7-11 carbon atom aryl acyl group; the aroyl of 7-11 the carbon atom that replaces; wherein the substituting group of tertiary alkyl is the tertiary alkyl peroxy of 4-8 carbon atom; and the substituting group of aroyl is the low alkyl group of one or more 1-4 carbon atom; the alkoxyl group of 1-4 carbon atom; phenyl; the acyloxy of 2-8 carbon atom; the tertiary alkyl peroxide carbonyl of 5-9 carbon atom; fluorine; chlorine; or bromine, and R ⁹Can also be structural formula (b), (c) and (d)

In the formula, x is 0 or 1, R ¹¹Be the alkyl of a replacement or a unsubstituted 1-18 carbon atom, its substituting group is the alkyl of one or more 1-6 carbon atom, the tertiary alkyl peroxy of a 4-8 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, hydroxyl, chlorine, bromine or the cyano group of a 6-10 carbon atom; Or the replacement of 5-12 carbon atom or unsubstituted cycloalkyl, it is the low alkyl group of one or more 1-4 carbon atom that one or more Sauerstoffatoms or nitrogen-atoms and its substituting group can randomly be arranged on naphthenic ring, and

R ¹²Be the replacement or the unsubstituted divalent alkyl of 2-3 carbon atom, its substituting group is the low alkyl group of one or more 1-4 carbon atom; Or replacement or unsubstituted divalence 1,2-, 1,3-or 1,4-phenylene, its substituting group are low alkyl group, chlorine, bromine, nitro or the carboxyl of one or more 1-4 carbon atom, and,

R ¹³Be the low alkyl group of 1-4 carbon atom, two R in addition ¹³Base also can connect together and form the divalent alkyl of 4-5 carbon atom, R ¹⁴Be the low alkyl group of 1-4 carbon atom, R ¹⁵, R ¹⁶And R ¹⁷Be selected from the alkyl of hydrogen, a 1-8 carbon atom, the aryl of a 6-10 carbon atom, the alkoxyl group of a 1-8 carbon atom and the aryloxy of 6-10 carbon atom,

Preferably, R is selected from down group: H; The alkyl of a replacement or a unsubstituted 1-22 carbon atom, its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, fluorine, chlorine, bromine, carboxyl and the cyano group of a 6-10 carbon atom; The aralkyl of a replacement or a unsubstituted 7-13 carbon atom, its substituting group is the alkyl of one or more 1-6 carbon atom; The cycloalkyl of a replacement or a unsubstituted 5-12 carbon atom, its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-14 carbon atom replaces or unsubstituted bicyclic alkyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; The replacement of 7-16 carbon atom or unsubstituted tricyclic alkyl, its substituting group are the low alkyl group of one or more 1-4 carbon atom; And structure (a),

More preferably, R is selected from down group: H; The alkyl of a replacement or a unsubstituted 1-22 carbon atom, its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, chlorine, bromine, carboxyl and the cyano group of a 6-10 carbon atom; The cycloalkyl of a replacement or a unsubstituted 5-12 carbon atom, its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-14 carbon atom replaces or unsubstituted bicyclic alkyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; And structure (a), and

R ⁶Be selected from: unsubstituted 4-12 carbon atom tertiary alkyl, 4-12 carbon atom tertiary alkyl of replacement, uncle's cycloalkyl of a 6-13 carbon atom, uncle's alkynyl of a 5-9 carbon atom and uncle's aralkyl of 9-13 carbon atom, wherein the substituting group of tertiary alkyl is the tertiary alkyl peroxy of 4-8 carbon atom

Preferably, Q and Q ¹Can be identical or different, they are selected from chlorine, bromine and R-O, more preferably Q and Q ¹Be identical, they are selected from chlorine and R-O.

Aspect method, the invention provides the free radical addition of the unsaturated substrate of olefinic is reacted the method that causes, this method is selected from down group:

As solidifying agent, to the novel method that unsaturated polyester resin compositions is cured, it is by in the presence of the superoxide material of the structural formula A of initiation amount, heats this resin under suitable temperature with the superoxide material of structural formula A; With

The superoxide material of structural formula A is used as radical initiator, ethylenically unsaturated monomer (as vinylbenzene, ethene, vinylchlorid, glycol ether two (allyl carbonate) (ADC) etc.) is carried out the polymeric novel method, and it is by using the superoxide material of the structural formula A of initiation amount under the suitable temperature.

Two (one-and two-cross barkites) compound-preparation method of novel structural formula A

The preparation of two (one-and two-cross barkites) compound of novel structural formula A can be passed through: with the dihydro-peroxidase of structural formula B,

With the halo oxalic acid tertiary alkyl peroxy ester of oxalyl halogen, chloro oxalic acid alkyl ester or structural formula C,

(X=Br or Cl in the formula; Q (or Q ¹)=Br, Cl, R-O or R ⁶-OO)

Under-90 to 50 ℃ temperature, mineral alkali or organic bases exist or do not exist and one or more solvents exist or non-existent condition under react.The material of structural formula C can be an oxalyl halogen, as when X and Q are Br and Cl, is exactly oxalyl bromine and oxalyl chloride.When X is Br or Cl and Q when being R-O, the material of structural formula C is exactly a halo oxalic acid alkyl ester.As X being Br or Cl and Q is R ⁶During-OO, structural formula C material is exactly a halo oxalic acid tertiary alkyl peroxy ester.

The indefiniteness example of suitable optional solvents comprises: pentane, hexane, heptane, dodecane, the white spirits mixture of odorless, toluene, dimethylbenzene, isopropyl benzene, methylene dichloride, ethyl acetate, acetate 2-ethylhexyl, isobutyl isobutyrate, dimethyl adipate, Succinic acid dimethylester, Methyl glutarate (or its mixture), rutgers, phthalic acid dibutyl ester, phthalic acid benzyl butyl ester, diethyl ether, methyl tertiary butyl ether, acetate 2-methoxyl group ethyl ester etc.

The indefiniteness example of suitable optional alkali comprises: triethylamine, Tributylamine, N, N-diisopropylethylamine, 2,2,6,6-tetramethyl piperidine, N, accelerine, N, N-dimethyl aminopyridine, 2,4, and the 6-trimethylpyridine (collidine, colidine), urea, tetramethyl-urea, sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, salt of wormwood, saleratus, calcium hydroxide, magnesium hydroxide, hydrated barta, lime carbonate and tertiary sodium phosphate.

Can react with the compound of structural formula C, the dihydro-peroxidase indefiniteness example of suitable structural formula B comprises: 2,5-dimethyl-2,5-two hydroperoxy hexanes, 2,5-dimethyl-2,5-two hydroperoxies-3-hexin, 3,6-dimethyl-3,6-two hydroperoxy octanes, 3,6-dimethyl-3,6-two hydroperoxies-4-octyne, 2,7-dimethyl-2,7-two hydroperoxy octanes, 2,7-dimethyl-2,7-two hydroperoxies-3, the hot diine of 5-, 1,3-diisopropyl benzene dihydro-peroxidase, 1,4-diisopropyl benzene dihydro-peroxidase, with 1,3,5-triisopropylbenzene three hydroperoxide.

The indefiniteness example of suitable oxalic acid halogen comprises: oxalyl bromine and oxalyl chloride.Can with the dihydro-peroxidase of structural formula B structural formula C (X=Br or Cl reaction, suitable; Q=R-O) halo oxalic acid alkyl ester indefiniteness example comprises: chloro methyl oxalate (being also referred to as methyl oxalyl chloride and chloroethene aldehydic acid methyl esters), the bromo ethyl oxalate, the chloro ethyl oxalate, chloro oxalic acid isopropyl ester, the positive butyl ester of chloro oxalic acid, the chloro oxalic acid tert-butyl ester, chloro oxalic acid 2-ethylhexyl, chloro oxalic acid dodecyl ester, chloro oxalic acid cetyl ester, chloro oxalic acid docosyl ester, chloro oxalic acid 2,2, the 2-trifluoro ethyl ester, chloro oxalic acid allyl ester, chloro oxalic acid phenyl ester, chloro oxalic acid 2-phenoxy ethyl, the chloro cyclohexyl oxalate, chloro oxalic acid 4-tertiary butyl cyclohexyl, chloro oxalic acid  ester, chloro oxalic acid isobornyl thiocyanoacetate, chloro oxalic acid norbornene ester, outside the chloro oxalic acid-the norborneol ester, in the chloro oxalic acid-the norborneol ester, chloro oxalic acid 1-diamantane ester (l-adamantyl chlorooxalate), chloro oxalic acid 2-diamantane ester, chloro grass acid benzyl ester, chloro oxalic acid 3-t-butylperoxy-1,3-dimethyl butyl ester and chloro oxalic acid 3-(2-ethyl hexanoyl peroxy)-1,3-dimethyl butyl ester.Can by with the oxalyl bromine of excessive 0-100% or oxalyl chloride and corresponding reaction of alkanol until the reaction end, and obtain above-mentioned halo oxalic acid alkyl ester.Remove excessive oxalyl halogen by stripping or distillation.Can with oxalyl halogen reaction with the halo oxalic acid alkyl ester that forms structural formula C, suitable alkanol indefiniteness example comprises: methyl alcohol, ethanol, Virahol, the trimethyl carbinol, propyl carbinol, 2-Ethylhexyl Alcohol, dodecanol, cetyl alcohol, V-1326, the hexafluoro amylalcohol, 2,2, the 2-trifluoroethanol, vinyl carbinol, hexalin, 4-tertiary butyl hexalin, menthol, outward-2-Norborneol, in-2-Norborneol, borneol alcohol, iso-borneol alcohol, the 1-adamantanol, the 2-adamantanol, phenol, the 2-phenoxyethyl alcohol, benzylalcohol, 3-t-butylperoxy-1, the pure and mild 2-ethyl of 3-dimethyl butyrate peroxy caproic acid 3-hydroxyl-1,1-dimethyl butyl ester.

Can be by randomly in the presence of one or more solvents, excessive oxalyl halogen such as oxalyl bromine or oxalyl chloride are reacted with the tertiary alkyl hydroperoxide, thereby prepare halo oxalic acid tertiary alkyl peroxy ester (X=Br or the Cl of structural formula C; Q=R ⁶-OO).By stripping or distillation, excessive oxalyl halogen and optional solvent are separated with halo oxalic acid tertiary alkyl peroxy ester.The example of the indefiniteness that optional solvents is suitable provides in the above.Halo oxalic acid tertiary alkyl peroxy tertiary alkyl hydroperoxide ester, the suitable indefiniteness example that is used to prepare structural formula C comprises: tert-butyl hydroperoxide, t-amyl hydroperoxide, uncle's hexyl hydroperoxide, 1,1,3,3-tetramethyl butyl hydroperoxide, 1-methylcyclohexyl hydroperoxide, to  alkane hydroperoxide, 2-hydroperoxy-2-methyl-3-butine, α-cumyl hydroperoxide and diisopropyl benzene one hydroperoxide.The indefiniteness example of suitable structural formula C halo oxalic acid tertiary alkyl peroxy esters comprises: chloro oxalic acid t-butylperoxy ester, chloro oxalic acid tert-pentyl peroxy ester, chloro oxalic acid 1,1,3,3-tetramethyl butyl peroxy esters and chloro oxalic acid sec.-propyl-α-cumyl peroxy esters.

As Q and Q ¹During for R-O, the compound of structural formula A has the route of synthesis of another kind of two steps, and it relates to earlier reacts the dihydro-peroxidase of structural formula B and excessive oxalyl halogen, then the structural formula D compound of excessive oxalyl halogen with novelty is separated:

There are suitable mineral alkali or organic bases and existing or not existing under the condition of solvent, with structural formula D compound and water or reaction of alkanol then.

The indefiniteness example of dihydro-peroxidase, mineral alkali or organic bases, optional solvents and the alkanol of suitable structural formula B is listed in the above.The structural formula D compound of suitable novelty comprises: 2,5-dimethyl-2,5-two (chloro carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (chloro carbonyl carbonyl peroxy)-3-hexin, 3,6-dimethyl-3,6-two (chloro carbonyl carbonyl peroxy) octane, 3,6-dimethyl-3,6-two (chloro carbonyl carbonyl peroxy)-4-octyne, 2,7-dimethyl-2,7-two (chloro carbonyl carbonyl peroxy) octane, 2,7-dimethyl-2,7-two (chloro carbonyl carbonyl peroxy)-3, the hot diine and 1 of 5-, 3-two (2-chloro carbonyl carbonyl peroxy-2-propyl group) benzene.

As Q and Q ¹Be R ⁶During-OO, the compound of structural formula A has the route of synthesis of another kind of two steps, it relates to the structural formula D compound that forms novelty earlier, then having suitable mineral alkali or organic bases and existing or do not exist under the condition of one or more solvents, with structural formula D compound and the reaction of tertiary alkyl hydroperoxide.

The indefiniteness example of structural formula D compound, mineral alkali or organic bases, optional solvents and the tertiary alkyl hydroperoxide of suitable novelty is listed in the above.

Novel structural formula A pair (one-and two-excessively barkites) compound-representative example

Except the example in illustrative embodiment, the indefiniteness example of two (one-and two-cross barkites) compound of novel structural formula A also comprises following material:

1,4-two (2-chloro carbonyl carbonyl peroxy-2-propyl group) benzene, 2,5-dimethyl-2,5-two (carboxyl carbonyl peroxy)-3-hexin, 2,5-dimethyl-2,5-two (chloro carbonyl carbonyl peroxy)-3-hexin, 2,5-dimethyl-2,5-two (methoxycarbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (methoxycarbonyl carbonyl peroxy)-3-hexin, 3,6-dimethyl-3,6-two (methoxycarbonyl carbonyl peroxy) octane, 3,6-dimethyl-3,6-two (methoxycarbonyl carbonyl peroxy)-4-octyne, 2,7-dimethyl-2,7-two (methoxycarbonyl carbonyl peroxy) octane, 2,7-dimethyl-2,7-two (methoxycarbonyl carbonyl peroxy)-3, the hot diine of 5-[wherein methoxycarbonyl carbonyl peroxy is following structure:

2,5-dimethyl-2,5-two (isopropoxy carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (n-butoxy carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (dodecyloxy carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (n-Hexadecane oxygen base carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (2,2,2-trifluoro ethoxy carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two [(2-phenoxy group oxyethyl group) carbonyl carbonyl peroxy] hexane, 2,5-dimethyl-2,5-two (allyloxy carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two (cyclohexyloxy carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two [(4-tertiary butyl cyclohexyloxy) carbonyl carbonyl peroxy)]-the 3-hexin, 2,5-dimethyl-2,5-two ( oxygen base carbonyl carbonyl peroxy) hexane, 2,5-dimethyl-2,5-two [(outer-norborneol oxygen base) carbonyl carbonyl peroxy)] hexane, 2,5-dimethyl-2,5-two [(1-Buddha's warrior attendant alkoxyl group) carbonyl carbonyl peroxy] hexane, 2,5-dimethyl-2,5-two [(2-Buddha's warrior attendant alkoxyl group) carbonyl carbonyl peroxy] hexane, 2,5-dimethyl-2,5-two (phenyloxycarbonyl carbonyl peroxy) hexane, 2,7-dimethyl-2,7 two (benzyloxycarbonyl carbonyl peroxy) octane, 2,5-dimethyl-2,5-two (benzyloxycarbonyl carbonyl peroxy)-3-hexin, 2,5-dimethyl-2,5-two [(3-t-butylperoxy-3-methyl butoxy) carbonyl carbonyl peroxy] hexane, 2,5-dimethyl-2,5-two [{ 3-(2-ethyl hexanoyl peroxy)-1,3-dimethyl butoxy } the carbonyl carbonyl peroxy] hexane, 2,7-dimethyl-2,7-two (borneol oxygen base carbonyl carbonyl peroxy) octane, 1,3-two [1-methyl isophthalic acid-(dodecyloxy carbonyl carbonyl peroxy) ethyl] benzene, 1,4-two [1-methyl isophthalic acid-(hexyloxy carbonyl carbonyl peroxy) ethyl] benzene, 1,3,5-three [1-methyl isophthalic acid-(oxygen base carbonyl carbonyl peroxy in the last of the ten Heavenly stems) ethyl] benzene, 2,5-dimethyl-2,5-two (t-butylperoxy carbonyl carbonyl peroxy)-3-hexin, with 2,5-dimethyl-2,5-two (tert-pentyl peroxy carbonyl carbonyl peroxy) hexane.

Novel structural formula A pair (one-and two-excessively barkites) compound-purposes

A. polymerization ethylenically unsaturated monomer

Under suitable temp and pressure ethylenically unsaturated monomer is carried out radical polymerization, the superoxide of finding the structural formula A of novelty of the present invention is initiator (reducing the demand of initiator etc.) efficiently aspect efficient.Ethylenically unsaturated monomer comprises: alkene, as ethene, propylene, vinylbenzene, alpha-methyl styrene, p-methylstyrene, chloro-styrene, bromstyrol, vinyl chloride, vinyl pyridine and Vinylstyrene; Diolefine is as 1,3-butadiene, isoprene and chloroprene; Vinyl ester is as vinyl-acetic ester, propionate, vinyl laurate, vinyl benzoate and divinyl carbonate; Unsaturated nitrile is as vinyl cyanide and methacrylonitrile; Vinylformic acid and methacrylic acid and their acid anhydrides, ester and acid amides, as acrylic anhydride, and the allyl ester of vinylformic acid and methacrylic acid, methyl esters, ethyl ester, positive butyl ester, 2-hydroxy methacrylate, glycidyl ester, lauryl and 2-ethylhexyl, and acrylamide and Methacrylamide; Maleic anhydride and itaconic anhydride; Toxilic acid, methylene-succinic acid and fumaric acid and their ester; Vinyl halide and vinylidene dihalide are as vinylchlorid, bromine ethene, vinyl fluoride, vinylidene chloride and vinylidene fluoride; Perhalogeno alkene is as tetrafluoroethylene, R 1216 and chlorotrifluoroethylene; Vinyl ether is as methylvinylether, ethyl vinyl ether and n-butyl vinyl ether; Allyl ester, as allyl acetate, phenylformic acid allyl ester, carbonic acid allyl ethyl ester, triallyl phosphate, dially phthalate, diallyl fumarate, pentanedioic acid diallyl, diallyl adipate, carbonic acid diallyl, two (allyl carbonate) (they being ADC) of glycol ether; Propenal; Methyl vinyl ketone; Or their mixture.

In the conventional polyreaction and copolymerization of ethylenically unsaturated monomer, the general condition that adopts is that temperature is 0-100 ℃, preferably be 20-90 ℃, more preferably be 30-75 ℃, and the concentration of structural formula A two (one-and two-cross barkites) (pure) is the 0.002-10% of monomer weight or more, preferably being 0.005-2%, more preferably is 0.01-1%.The superoxide synthetics of novelty of the present invention can use with other other radical initiators, as at United States Patent (USP) 4,525, and disclosed initiator above below, the 4th hurdle and the 5th hurdle in 308 (on June 25th, 85, the authorizing Pennwalt Corporation).Superoxide synthetics of the present invention and these initiators be used in combination make the technology of polymer producers that greater flexibility is arranged, and can make them can " finely tune " their polymerization technique.

B. solidify unsaturated polyester resin

In the presence of free radical curing agent, by heating under proper curing temperature in the process of cure unsaturated polyester resins composition, compound shows the structural formula A of novelty of the present invention two (-and two-cross barkites) that higher curing activity is arranged in curable unsaturated polyester resin compositions.Two (one-and two-cross barkites) compound solidified of available novelty of the present invention, unsaturated polyester resin comprise: undersaturated polyester and one or more ethylenically unsaturated monomers.

For example; undersaturated polyester is by to undersaturated binary of at least a olefinic or polycarboxylic acid; acid anhydrides or acyl halide; as toxilic acid; fumaric acid; propene dicarboxylic acid; methylene-succinic acid; methylfumaric acid; citraconic acid; allyl malonic acid; tetrahydrophthalic acid etc.; with saturated or undersaturated binary or polyvalent alcohol such as ethylene glycol; glycol ether; triglycol; 1; 2-and 1; ammediol; 1; 2-; 1,3-and 1,4-butyleneglycol; 2; 2-dimethyl-1; ammediol; 2-hydroxymethyl-2-methyl isophthalic acid, ammediol; 2-butylene-1, the 4-glycol; 2-butyne-1; the 4-glycol; 2; 4,4-trimethylammonium-1,3-pentanediol; glycerine; tetramethylolmethane; N.F,USP MANNITOL etc. carry out esterification and the polyester that obtains.Also can use the mixture of these diprotic acid or polyprotonic acid and/or the mixture of these dibasic alcohol or polyvalent alcohol.These binary or polycarboxylic acid can part be replaced by saturated binary or polycarboxylic acid such as hexanodioic acid, succsinic acid, sebacic acid etc. and/or by the binary of aromatics or polycarboxylic acid such as phthalic acid, trimellitic acid, 1,2,4,5-pyromellitic acid, m-phthalic acid and terephthalic acid are replaced.These acid can be replaced by the group such as halogen atom.The example of this suitable halogenated acid for example has: tetrachlorophthalic acid, tetrabromophthalate, 5,6-dicarboxyl-1,2,3,4,7,7-chlordene two ring (2.2.1)-2-heptene etc.

Other components of unsaturated polyester resin compositions, polymerisable monomer, be preferably ethylenically unsaturated monomer, as vinylbenzene, alpha-methyl styrene, p-methylstyrene, chloro-styrene, bromstyrol, vinyl chloride, Vinylstyrene, diallyl maleate, dibutyl fumarate, triallyl phosphate, triallyl cyanurate, Phthalic acid, diallyl ester, diallyl fumarate, methyl acrylate, methyl methacrylate, n-butyl acrylate, n-BMA, ethyl propenoate etc., or their mixture, these ethylenically unsaturated monomers can carry out copolymerization with this undersaturated polyester.

Preferred unsaturated polyester resin compositions contains, as 1 of unsaturated polyester component, the esterification products of 2-propylene glycol (many alcohol), maleic anhydride (acid anhydrides of unsaturated polycarboxylic acid) and Tetra hydro Phthalic anhydride (acid anhydrides of aromatic dicarboxylic acid), and as the vinylbenzene of monomer component.

The unsaturated polyester resin compositions of other types can be cured the superoxide synthetics of novelty of the present invention as curing catalysts.The resin that is called unsaturated ethylene thiazolinyl ester resin is made of vinyl ester resin part and a kind of or how secondary polymerisable monomer component.The preparation of vinyl ester resin component can be passed through: with chlorine epoxide such as Epicholorohydrin, with an amount of bis-phenol such as dihydroxyphenyl propane [2,2-(4-hydroxy phenyl) propane], in the presence of alkali such as sodium hydroxide, react, thereby produce condensation product with terminal epoxy groups (from chlorine epoxide).Subsequently with this condensation product and polymerisable unsaturated carboxylic acid such as vinylformic acid and methacrylic acid, under the existence of acidity or basic catalyst or non-existent condition, react, form the vinyl ester resin component.Generally, vinylbenzene is added as the polymerisable monomer component, to finish the preparation of unsaturated ethylene thiazolinyl ester resin composition.

The general temperature that adopts is about 20-200 ℃, and novel structural formula A two (-and two-cross barkites) compound concentrations is about 0.05-5% of curable unsaturated polyester resin compositions weight or more, preferably being 0.10-4%, more preferably is 0.25-3%.

Can add various materials in the above-mentioned unsaturated polyester resin compositions, as sulphur, glass, carbon and boron fibre, carbon black, silicon oxide, metal silicate, clay, metal carbonate, antioxidant (AO), thermo-stabilizer, ultraviolet ray (UV) stablizer and photostabilizer, sensitizing agent, dyestuff, pigment, setting accelerator, metal oxide such as zinc oxide, whipping agent, nucleator etc.

C. solidify allyl diglycol carbonates (ADC) resin

In the presence of free radical curing agent, under proper curing temperature, solidify by heating ADC monomer or two (allyl carbonate) processes (ADC) of polymerization glycol ether in,

The structural formula A of novelty of the present invention two (one-and two-cross barkites) compound shows curing or the polymerization activity higher to the ADC monomer composition.The ADC that adds can be the commercially available CR-39 monomer as Pittsburgh Plate GlassCompany (PPG) (CAS Reg.No.142-22-3), also can produce (R.Dowbenko with the reaction of vinyl carbinol in the presence of alkali by glycol ether two (chloro-formic ester), edit at J.I.Kroschwitz and M.Howe-Grant, KirK-Othmer-Encyclopedia of Chemical Technology; " AllylMonomers and Polymers "; the 4th edition; vol.2; Wiley-Interscience Publication, JohnWiley﹠amp; Sons, Inc., New York 1992, pp 163-168).The ADC monomer can solidify separately or polymerization; also can with other comonomers such as acrylate, methacrylic ester, allyl ester, dicarboxylic acid diallyl (as Phthalic acid, diallyl ester), maleic anhydride and other monomers solidify or polymerization, thus colourless, transparent, firm, anti-fragmentation and solvent-proof mold or lens produced.The curing of ADC monomer composition or polymerization generally use substance law (not having solvent) to carry out.Generally, curing or polymerization ADC monomer composition divide 2 stages to carry out to form cast sheet or lens.Fs is the major portion of polyreaction, it be curing initiator (being generally two carbonic acid lower dialkyl esters (lower dialkyl peroxydicarbonate)) exist and 35-120 ℃ temperature under carry out.Curing or polymerization time are about 5-50 hour.Usually, adopt time temperature curve in this fs.Provided a time temperature curve example below:

Be used to solidify the typical solidification value table of ADC

Time (hour)	Temperature (℃)
Time (hour)	Temperature (℃)	0.0	61
1.0	62	0.0	61
1.0	62	3.0	64
7.0	69	3.0	64
7.0	69	8.0	69
8.5	74	8.0	69
8.5	74	9.0	79
9.5	86.5	9.0	79
9.5	86.5	10.0	96.5
10.5	445	10.0	96.5
10.5	445	10.75	85
11.0	60	10.75	85
11.0	60	11.25	40
11.5	30	11.25	40

The curing of ADC monomer composition or polymeric subordinate phase are after fixing or the annealing of under 100-150 ℃ the ADC resin being carried out one or more hours.The example of an after fixing ADC resin is to carry out 2 hours at 115 ℃.

General novel two (one-and two-cross barkite) compound concentrations that adopts is about 1-6% curable or polymerisable ADC monomer composition weight or more, preferably is 2-5%, more preferably is 2.5%-4%.

Can add various materials in the above-mentioned ADC resin combination, as antioxidant (AO), thermo-stabilizer, ultraviolet ray (UV) stablizer and photostabilizer, toning agent (tints), photochromic additive and dyestuff.In addition, the low molecular weight propylene acid resin that the ADC resin combination also can contain such as acrylate copolymer and anti-contraction (is disclosed in United States Patent (USP) 4,217,433 (on Augusts 12nd, 80, authorize Pennwalt Corporation, belong to ElfAtochem North America now, Inc.)) and so on additive.14% shrinking percentage that this anti-shrink additives takes place when can be used for offsetting the ADC monomer polymerization.

Novel structural formula A pair (one-and two-excessively barkites) compound-preparation embodiment and purposes embodiment

The following example is used to set forth the enforcement best mode of the present invention of contriver's design, and they are used to provide the detailed preparation of the present invention and the content of use aspect, but they are not limited to scope of the present invention.

Embodiment 1

Preparation 2,5-dimethyl-2,5-two (ethoxy carbonyl carbonyl peroxy) hexane (I-1)

In this embodiment, in the presence of pyridine, with chloro ethyl oxalate and 2,5-dimethyl-2, the reaction of 5-two hydroperoxy hexanes, to obtain this product:

In 500 milliliters of reactors mechanical stirrer, thermometer and feed hopper, the band water jacket are housed, add 200 milliliters of methylene dichloride, 7.2 gram (40.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 7.0 gram (88.0 mmole) pyridines.Stirred mixture is cooled to 0 ℃, in 10-15 minute, restrains the solution of (82.0 mmole) 98% chloro ethyl oxalates in 40 milliliters of methylene dichloride then to wherein slowly adding 11.8.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 0-10 ℃, added 50 ml waters then, and 5 ℃ of restir reactive material 10 minutes.Then with the upper strata water separately, organic layer washs with 40 milliliter of 5% hydrochloric acid soln, then with each 100 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 12.7 grams (84.1% theoretical value is revised) colourless liquid.The IR spectrum of this product shows, at 3500cm ^-1There is little OH band in the zone.At 1780cm ^-1The place has one to cross barkite carbonyl master band, at 1735cm ^-1There is oxalic acid carbonyl ester group master band at the place.Rapid Thermal test (J.Varjavandi and O.L.Mageli, J.Chem.Ed.48, A451 (1971)) result of this product is 45 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 7.47% active oxygen (theoretical value, 8.46%), so the product analysis result is 88.3% that revising productive rate is 74.3%.

According to preparation method, productive rate data (analytical results and revised productive rate), Rapid Thermal data and infrared spectrum data, the product that obtains in this reaction is exactly required title product.

Embodiment 2

Preparation 2,5-dimethyl-2,5-two (docosane oxygen base carbonyl carbonyl peroxy) hexane (I-2)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, V-1326 and excessive 50% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced chloro oxalic acid docosane ester, and its analytical results is 91.4%, and revised productive rate is 92.5%.In second step, chloro oxalic acid docosane ester and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, and to produce this product, its specific descriptions are as follows:

In 500 milliliter of three neck reactor of magnetic stirring bar, condenser, thermometer and feed hopper is housed, add 60 milliliters of pentanes, 2.0 gram (11.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 2.4 gram (30.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (22.0 mmole) 91.4% chloro oxalic acid docosane esters in 250 milliliters of pentanes to wherein slowly adding 10.0 then in 20 minutes.After add finishing, reactive material stirred 90 minutes at 0 ℃, added 100 ml waters and 100 milliliters of hexanes then, and 5 ℃ of restir reactive material 10 minutes.Then with lower floor's water separately, organic layer is 7.0 with 5% hydrochloric acid soln and water washing until the pH with water washing liquor later.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 6.7 grams (65% theoretical value is revised) white solid, and its fusing point is 71 ℃.The IR spectrum of this product during as Nujol mull shows, at 3500cm ^-1The no OH band in zone.At 1775cm ^-1The place has one to cross barkite carbonyl master band.The Rapid Thermal test result of this product is 72 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 3.21% active oxygen (theoretical value, 3.41%), so the product analysis result is 94.1% that revising productive rate is 61.2%.

According to preparation method, productive rate data, Rapid Thermal data and infrared spectrum data, the product that obtains in this reaction is exactly required title product.

Embodiment 3

Preparation 2,5-dimethyl-2,5-two [(4-tertiary butyl cyclohexyloxy) carbonyl carbonyl peroxy] hexane (I-3)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, 4-tertiary butyl hexalin and excessive 50% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced chloro oxalic acid 4-tertiary butyl cyclohexyl, and its analytical results is 96.9%, and revised productive rate is 95.3%.In second step, chloro oxalic acid 4-tertiary butyl cyclohexyl and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, to produce this product:

In 500 milliliters of reactors mechanical stirrer, thermometer and feed hopper, the band water jacket are housed, add 75 milliliters of methylene dichloride, 3.6 gram (20.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 3.5 gram (44.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (40..0 mmole) 96.9% chloro oxalic acid 4-tertiary butyl cyclohexyls in 25 milliliters of methylene dichloride to wherein slowly adding 9.9 then in 10-15 minute.After add finishing, reactive material stirred 60 minutes at 0-10 ℃, added 50 ml waters then, and 5 ℃ of restir reactive material 10 minutes.Then with the upper strata water separately, organic layer washs with 20 milliliter of 5% hydrochloric acid soln, then with each 50 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 13.7 grams (＞100% theoretical value is revised) colourless liquid.The IR spectrum of this product shows, at 1790cm ^-1The place has one to cross barkite carbonyl master band, at about 1750cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 57 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 3.88% active oxygen (theoretical value, 5.34%), so the product analysis result is 72.7% that revising productive rate is 83%.

Embodiment 4

Preparation 2,5-dimethyl-2,5-two (iso-borneol oxygen base carbonyl carbonyl peroxy) hexane (I-4)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, iso-borneol alcohol and excessive 50% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced chloro oxalic acid isobornyl thiocyanoacetate, and its analytical results is 95.2%, and revised productive rate is 91.3%.In second step, chloro oxalic acid isobornyl thiocyanoacetate and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, and to produce this product, its specific descriptions are as follows:

In 500 milliliters of reactors mechanical stirring rod, thermometer and feed hopper, that have water jacket are housed, add 100 milliliters of methylene dichloride, 3.6 gram (20.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 3.5 gram (44.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (40.0 mmole) 95.2% chloro oxalic acid isobornyl thiocyanoacetates in 20 milliliters of methylene dichloride to wherein slowly adding 10.3 then in 10-15 minute.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 0-10 ℃, added 50 ml waters then, and 5 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer washs with 20 milliliter of 5% hydrochloric acid soln, then with each 50 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filter removing the exhausted siccative, solvent removed in vacuo obtains the colourless liquid of about 20 gram viscosity.In this product, add 50 milliliters of pentanes, so that be settled out a solid product.Mixture is cooled to-20 ℃, solid by filtration is separated and dry air.Obtain 7.2 grams (60.5% theoretical value is not revised) white solid, its fusing point is 78-80 ℃.The IR spectrum of this product during as Nujol mull shows, at 3500cm ^-1The no obvious OH band in zone.At 1785cm ^-1The place has one to cross barkite carbonyl master's band and at 1735cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 63 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 5.08% active oxygen (theoretical value, 5.38%), so the product analysis result is 94.4% that revising productive rate is 57.1%.

Find 2,5-dimethyl-2,5-two (iso-borneol oxygen base carbonyl carbonyl peroxy) the 10 hour half life temperatures of hexane (I-4) in trieline are 20 ℃, therefore cross barkite with the OO-tertiary alkyl O-alkyl one of prior art and compare, and I-4 is active high superoxide.

Embodiment 5

Preparation 2,5-dimethyl-2,5-two (neopentyl oxygen carbonyl carbonyl peroxy) hexane (I-5)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, neopentyl alcohol and excessive 50% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced chloro oxalic acid peopentyl ester, and its analytical results is 100%, and revised productive rate is 92.7%.In second step, chloro oxalic acid peopentyl ester and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, and to produce this product, its specific descriptions are as follows:

Refrigerative in ice-water bath, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, add 60 milliliters of MTBE, 3.6 gram (20.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 4.5 gram (57.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (42.0 mmole) 100% chloro oxalic acid peopentyl esters in 10 milliliters of MTBE to wherein slowly adding 7.5 then in 10-15 minute.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters then, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 9.1 grams (97.8% theoretical value is revised) white solid, and its fusing point is 35-37 ℃.The IR spectrum of this product during as Nujol mull shows, at 3500cm ^-1The no tangible OH band in zone.At 1790cm ^-1The place has one to cross barkite carbonyl master's band and at about 1740cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 54 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 6.66% active oxygen (theoretical value, 6.92%), so the product analysis result is 96.2% that revising productive rate is 94.2%.

Embodiment 6

Preparation 2,5-dimethyl-2,5-two (neopentyl oxygen carbonyl carbonyl peroxy)-3-hexin (I-6)

In this embodiment, earlier with anhydrous magnesium sulfate drying wet, 78%2,5-dimethyl-2, the 5-two hydroperoxies-solution of 3-hexin in MTBE, then filtering separation is fallen the exhausted siccative, then with anhydrous 2,5-dimethyl-2,5-two hydroperoxies-3-hexin solution reacts with chloro oxalic acid peopentyl ester in the presence of pyridine, and to prepare this product, its specific descriptions are as follows:

4.5 gram (0.020 mole) wet 78%2,5-dimethyl-2, the solution of 5-two hydroperoxies-3-hexin in 60 milliliters of MTBE is with 5 weight % anhydrous magnesium sulfate dryings.Solution filter and with 3 parts 10 milliliters fresh MTBE washing filters on after the exhausted sal epsom, the MTBE of merging is added in refrigerative in the ice-water bath, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper.Add 4.5 gram (0.057 mole) anhydrous pyridines.The inclusion of flask is cooled to 0 ℃, in 10-15 minute, in about 0 ℃ of solution that form, vigorous stirring, slowly adds the solution of 7.5 gram (0.042 mole) 100% chloro oxalic acid peopentyl esters in 10 milliliters of MTBE then.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters then, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 10.0 grams (＞100% theoretical value is revised) liquid.The IR spectrum of this product shows, at 3500cm ^-1There is a little OH band in the zone, at about 1800cm ^-1The place has one to cross barkite carbonyl master's band and at about 1750cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 54 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 6.39% active oxygen (theoretical value, 6.98%), so the product analysis result is 91.5% that revising productive rate is 99.5%.

Embodiment 7

Preparation 2,5-dimethyl-2,5-two (borneol oxygen base carbonyl carbonyl peroxy) hexane (I-7)

In this embodiment, with 98%2 among the MTBE, 5-dimethyl-2,5-two hydroperoxy hexanes and 96.6% chloro oxalic acid norbornene ester react in the presence of pyridine, to prepare this product.Chloro oxalic acid norbornene ester is by with borneol alcohol and excessive oxalul chloride reaction, removes HCl then and excessive oxalul chloride prepares.Specific procedure is as follows:

Refrigerative in ice-water bath, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, add 60 milliliters of MTBE, 3.6 gram (20.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 4.5 gram (57.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (42.0 mmole) 96.6% chloro oxalic acid norbornene esters in 10 milliliters of MTBE to wherein slowly adding 10.6 then in 10-15 minute.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters then, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 7.4 grams (62.2% theoretical value is revised) white solid, and its fusing point is 80 ℃.The IR spectrum of this product during as Nujol mull shows, at 3500cm ^-1The no tangible OH band in zone.At 1790cm ^-1The place has one to cross barkite carbonyl master's band and at about 1745cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 54 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 5.02% active oxygen (theoretical value, 5.38%), so the product analysis result is 93.3% that revising productive rate is 58.8%.

Embodiment 8

Preparation 2,5-dimethyl-2,5-two (benzyloxycarbonyl carbonyl peroxy) hexane (I-8)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, benzylalcohol and excessive 50% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced chloro grass acid benzyl ester, and its analytical results is 96.6%, and revised productive rate is 92.1%.In second step, chloro grass acid benzyl ester and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, and to produce this product, its specific descriptions are as follows:

Refrigerative in ice-water bath, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, add 60 milliliters of MTBE, 3.6 gram (20.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 4.5 gram (57.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (42.0 mmole) 96.6% chloro grass acid benzyl esters in 10 milliliters of MTBE to wherein slowly adding 8.6 then in 10-15 minute.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters then, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 6.2 grams (61.4% theoretical value is revised) white solid, and its fusing point is 60-61 ℃.The IR spectrum of this product during as Nujol mull shows, at 3500cm ^-1The no tangible OH band in zone.At 1785cm ^-1The place has one to cross barkite carbonyl master's band and at about 1740cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 72 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 6.14% active oxygen (theoretical value, 6.37%), so the product analysis result is 96.4% that revising productive rate is 59.2%.

Embodiment 9

Preparation 2,5-dimethyl-2,5-two (tert-butoxycarbonyl carbonyl peroxy) hexane (I-9)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, the trimethyl carbinol and excessive 50% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced the chloro oxalic acid tert-butyl ester, and its analytical results is 100%, and revised productive rate is 90.8%.In second step, the chloro oxalic acid tert-butyl ester and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, and to produce this product, its specific descriptions are as follows:

Refrigerative in ice-water bath, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, add 60 milliliters of MTBE, 3.6 gram (20.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 4.5 gram (57.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (42.0 mmole) 100% chloro oxalic acid tert-butyl esters in 10 milliliters of MTBE to wherein slowly adding 6.9 then in 10-15 minute.Beginning just to have formed a solid, i.e. pyridinium chloride soon after the adding.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters then, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 4.5 grams (51.7% theoretical value is revised) product liquid.The IR spectrum of this product shows, at 3500cm ^-1The no tangible OH band in zone.At 1785cm ^-1The place has one to cross barkite carbonyl master's band and at about 1740cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 33 ℃, and this has confirmed that this product is very cryogenic superoxide.

According to preparation method, Rapid Thermal data and infrared spectrum data, the product that obtains in this reaction is exactly required title product.

Embodiment 10

Preparation 2,5-dimethyl-2,5-two (hexafluoro pentyloxy carbonyl carbonyl peroxy) hexane (I-10)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, hexafluoro amylalcohol and excessive 100% mole oxalyl chloride reaction.After reaction finished, excessive oxalul chloride stripped from product under reduced pressure, produced chloro oxalic acid hexafluoro pentyl ester, and its analytical results is 91.3%, and revised productive rate is 52.8%.In second step, chloro oxalic acid hexafluoro pentyl ester and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, and to produce this product, its specific descriptions are as follows:

Refrigerative in ice-water bath, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, add 60 milliliters of MTBE, 1.8 gram (10.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes and 2.3 gram (29.0 mmole) pyridines.To stir the mixture is cooled to 0 ℃, restrains the solution of (21.0 mmole) 91.3% chloro oxalic acid hexafluoro pentyl esters in 10 milliliters of MTBE to wherein slowly adding 6.6 then in 10-15 minute.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters then, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 5.5 grams (80.9% theoretical value is revised) product liquid.The IR spectrum of this product shows, at 1785cm ^-1The place has one to cross barkite carbonyl master's band and at about 1755cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 90 ℃, and this has confirmed that this product is cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 3.64% active oxygen (theoretical value, 4.72%), so the product analysis result is 77.1% that revising productive rate is 62.4%.

Embodiment 11

Preparation 2,5-dimethyl-2,5-two (chloro carbonyl carbonyl peroxy) hexane (I-11)

Refrigerative in ice-water bath is equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, adds 12.7 gram (0.100 mole) oxalyl chloride and 60 milliliters of MTBE.The inclusion of flask is cooled to 0 ℃.Then in 20 minutes, to form, divide lentamente in the solution of about 0 ℃ of vigorous stirring that to add 3.6 grams (0.020 mole) several times anhydrous 98%2,5-dimethyl-2,5-two hydroperoxy hexanes.Reaction was stirred 3 hours at 0 ℃ again.Add 7.2 gram diglymes then in product solution, then solvent removed in vacuo and excessive oxalyl chloride obtain the product solution (concentration about 50%) of 15.6 grams (＞100% theoretical value is not revised) in diglyme.The IR spectrum of this product solution shows, at 1790cm ^-1There was barkite carbonyl master band at the place.The Rapid Thermal test result of this product solution is 54-57 ℃, and this has confirmed that this product is very cryogenic superoxide.

Embodiment 12

Preparation 2,5-dimethyl-2,5-two (t-butylperoxy carbonyl carbonyl peroxy) hexane (I-12)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, tert-butyl hydroperoxide and excessive 100% mole oxalyl chloride reaction form chloro oxalic acid t-butylperoxy ester (A-1).

In second step, chloro oxalic acid t-butylperoxy ester (A-1) and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, to produce this product (I-12).

At room temperature, in 125 ml flasks, add 9.3 gram (100 mmole) 97% tert-butyl hydroperoxides, 75 milliliters of pentanes and 3 gram anhydrous magnesium sulfates.Stirred this inclusion 30 minutes, and then inclusion was filtered,, pentane washings and filtrate are merged with 25 milliliters of pentane washing exhausted sal epsom.Then refrigerative in ice-water bath is equipped with in the three-necked bottle of magnetic stirring bar, condenser, thermometer and feed hopper, adds 25.4 gram (200 mmole) oxalyl chloride and 25 milliliters of pentanes.Solution is cooled to 0 ℃.The anhydrous pentane solution that in 60 minutes, in the oxalyl chloride/pentane solution that stirs, slowly adds tert-butyl hydroperoxide then.Reaction was stirred 3 hours at 0 ℃ again, and vacuum is removed pentane and excessive oxalyl chloride under the frozen water temperature then, and (＞100% theoretical value is not revised to obtain 18.5 grams; Theoretical value is 18.1 grams) product liquid.The IR spectrum of this product shows, at 3500cm ^-1There is a very faint OH band at the place, and at 1797cm ^-1There is a unique mistake barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 45 ℃ (very loud cracklings), and this confirms that this product chloro oxalic acid t-butylperoxy ester is very cryogenic superoxide.Impact endurance test shock test (J.Varjavandi and O.L.Mageli, J.Chem.Ed.48, A451 (1971)) shows that this product is a shock-sensitive in the time of 3 inches, and impact is insensitive in the time of 1 inch.Because the heat sensitivity of this product and impact sensitivity, so the diglyme of weight such as use to dilute before using afterwards earlier.With the product after the diglyme dilution, its Rapid Thermal test result is that 60 ℃ (gentle decomposition) and shock-sensitive degree are on 20 inches.

In second step, using the ice bath refrigerative, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, add 1.8 gram (10.0 mmoles) 98%2,5-dimethyl-2,5-two hydroperoxy hexanes (anhydrous Luperox2,5-2,5), 2.3 gram (29.0 mmole) anhydrous pyridine and 60 milliliters of MTBE.Inclusion in the flask is cooled to 0 ℃.Then to form, in the solution of 0 ℃ of vigorous stirring, slowly add the solution of diglyme solution in 10 milliliters of MTBE of 7.7 gram (21.0 mmole) about 50% chloro oxalic acid t-butylperoxy esters.After add finishing, reactive material stirred 60 minutes at 0 ℃, added 10 ml waters afterwards, and 0-5 ℃ of restir reactive material 20 minutes.Then water layer is separated, organic layer is used each 75 milliliters of 5%NaHCO then with each 35 milliliter of 5% hydrochloric acid soln washing 3 times ₃Solution washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filter removing the exhausted siccative, add 4.7 gram diglymes as the height safe thinner that boils, and solvent removed in vacuo, (＞100% theoretical value is revised to obtain 8.7 grams; Theoretical value=4.7 grams) the screened stock material of product in diglyme.The IR spectrum of this product liquid shows, at 1769cm ^-1And 1801cm ^-1The place has 2 to cross barkite carbonyl master band.Product in diglyme, its Rapid Thermal test result is 51 ℃, this shows that this product is very cryogenic superoxide.

Embodiment 13

Preparation 2,5-dimethyl-2,5-two (3-t-butylperoxy-1,3-dimethyl butoxy carbonyl carbonyl peroxy) hexane (I-13)

In this embodiment, divide 2 synthesis steps to prepare product.In a first step, 3-t-butylperoxy-1,3-dimethyl butyrate alcohol and excessive 100% mole oxalyl chloride reaction.After reaction finishes, excessive oxalul chloride is stripped from product under reduced pressure, produce chloro oxalic acid 3-t-butylperoxy-1,3-dimethyl butyl ester, its analytical results are 97.5%, revised productive rate is 98.5%.In second step, chloro oxalic acid 3-t-butylperoxy-1,3-dimethyl butyl ester and 2,5-dimethyl-2,5-two hydroperoxy hexanes react in the presence of pyridine, to produce this product, specifically describe as follows:

Using the ice bath refrigerative, be equipped with in 250 milliliters of three-necked bottles of magnetic stirring bar, condenser, thermometer and feed hopper, it is anhydrous 98%2 to add 1.6 grams (9 mmole), 5-dimethyl-2,5-two hydroperoxy hexanes, 2.0 gram (25 mmole) anhydrous pyridine and 60 milliliters of MTBE.Inclusion in the flask is cooled to 0 ℃.Then to form, in the solution of about 0 ℃ of vigorous stirring, slowly add 5.2 gram (18 mmole) 97.5% chloro oxalic acid 3-t-butylperoxies-1, the solution of 3-dimethyl butyl ester in 10 milliliters of MTBE.After add finishing, reactive material stirred 60 minutes at 2 ℃, added 10 ml waters afterwards, and 3-4 ℃ of restir reactive material 10 minutes.Then water layer is separated, organic layer is with each 35 milliliter of 5% hydrochloric acid soln washing 3 times, then with each 75 ml waters washing 2 times.Product solution is with 5 weight % anhydrous magnesium sulfate dryings.After filtering removal exhausted siccative, solvent removed in vacuo obtains 6.5 grams (＞100% theoretical value is revised) product liquid.The IR spectrum of this product shows, at 3500cm ^-1The no OH band in zone.At about 1790cm ^-1The place has one to cross barkite carbonyl master's band and at about 1740cm ^-1There is barkite carbonyl master band at the place.The Rapid Thermal test result of this product is 54-57 ℃, and this has confirmed that this product is very cryogenic superoxide.According to the peroxy esters active oxygen method, records this product and contain 3.84% active oxygen (theoretical value, 4.80%), so the product analysis result is 80.0% that revising productive rate is 86.7%.

Embodiment 14

2,5-dimethyl-2,5-two (iso-borneol oxygen base carbonyl carbonyl peroxy) hexane (I-4) is 140 (60 ℃) SPI heat release data

The unsaturated polyester resin of Shi Yonging is the mixture of unsaturated polyester and styrene monomer in this embodiment.This unsaturated polyester is the Synolac for preparing by the following component of esterification:

Component	Quantity (mole)
Component	Quantity (mole)	Maleic anhydride	??1.0
Tetra hydro Phthalic anhydride	??1.0	Maleic anhydride	??1.0
Tetra hydro Phthalic anhydride	??1.0	Propylene glycol	??2.2

0.013 weight % quinhydrones inhibitor is joined in the resin of formation.The acid number of this Synolac is 45-50.Dilute the above-mentioned unsaturated polyester Synolac of 7 parts by weight with 3 parts by weight styrene monomers.The unsaturated polyester resin compositions that forms has following characteristic:

■ viscosity (Brookfied No.2 when 20r.p.m.)-13.0 pools

■ proportion-1.14

Cross two carbonic acid two (4-tert-butylcyclohexyl) esters (A-1) (a kind of commercially available peroxide product that is used for the cure unsaturated polyester resins composition), the peroxide neodecanoic acid tert-butyl ester (A-2) (another kind is used for the commercially available peroxide product of cure unsaturated polyester resins composition), two (one crosses barkite) compound 2 of peroxide neodecanoic acid α-cumyl (A-3) (a kind of commercially available low temperature peroxide initiator) and novelty of the present invention, 5-dimethyl-2, the gelation and the curing performance of 5-two (isobornyl oxygen base carbonyl carbonyl peroxy) hexane (I-4), SPI heat release program with standard is measured (the SPI program (Suggested SPI Procedure for RunningExotherm Curves-Polyester Resins) that is used for the suggestion of vibrin exotherm, be published in pre-printing-The 24th Annual TechnicalConference-reinforced Plastica/Composites Division, Society of the Plastics Industry, Inc., 1969).Use this program, at 140 °F (60 ℃), assessment is A-1, A-2, A-3 and I-4 relatively.The concentration of I-4 is 1.0 grams/100 gram virgin resin, and the concentration of A-1, A-2 and A-3 (per 100 gram resins) is equivalent to the concentration (pure) that active o content is 1.0 gram I-4.The result of this research provides in embodiment 14 data sheet, and it shows that I-4 makes resin gelization and solidified velocity ratio A-1, A-2 or A-3 faster.Therefore the peroxide catalyst of two (one crosses barkite) compound 3 kinds of commercially available lowest temperature of specific activity aspect cure unsaturated polyester resins of novelty of the present invention is much higher.

140 (60 ℃) SPI heat releases of embodiment 14 data sheet data
						Solidifying agent	Gram/100 gram resins	Gelation, minute	Solidify, minute	Exothermic peak, °F	Barcol hardness
????I-4	????1.0	????2.2	????3.6	????3.08	????35-40	Solidifying agent	Gram/100 gram resins	Gelation, minute	Solidify, minute	Exothermic peak, °F	Barcol hardness
????I-4	????1.0	????2.2	????3.6	????3.08	????35-40	????A-1	????1.29	????8.5	????11.4	????317	????35-40
????A-2	????0.82	????10.5	????13.8	????328	????35-40	????A-1	????1.29	????8.5	????11.4	????317	????35-40
????A-2	????0.82	????10.5	????13.8	????328	????35-40	????A-3	????1.03	????5.8	????7.7	????316	????35-40

Claims

1. two (-or two-cross barkites) of the structural formula A of a novelty:

R ⁵Be the divalent group that is selected from down group :-(CH ₂) _n-, in the formula n be 1-6 ,-C ≡ C-,-C ≡ C-C ≡ C-, 1,4-phenylene, replacement or unsubstituted 1,3-phenylene, its substituting group are following structure:

R preferably ⁵Be to be selected from-(CH ₂) _n-, in the formula n be 1-2 and-divalent group of C ≡ C-, more preferably R ⁵Be-(CH ₂) ₂-,

Q and Q ¹Be selected from down independently of one another group: chlorine, bromine, R-O and R ⁶-OO, wherein R is selected from down group: H; 1-24 carbon atom replaces or unsubstituted alkyl, and its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, fluorine, chlorine, bromine, carboxyl and the cyano group of a 6-10 carbon atom; 3-12 carbon atom replaces or unsubstituted alkenyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-10 carbon atom replaces or unsubstituted aryl, and its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, chlorine, bromine and the cyano group of a 6-10 carbon atom; 7-13 carbon atom replaces or unsubstituted aralkyl, and its substituting group is the alkyl of one or more 1-6 carbon atom; 5-12 carbon atom replaces or unsubstituted cycloalkyl, on naphthenic ring one or more oxygen or nitrogen-atoms can be arranged randomly, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-14 carbon atom replaces or unsubstituted bicyclic alkyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; The replacement of 7-16 carbon atom or unsubstituted tricyclic alkyl, its substituting group are the low alkyl group of one or more 1-4 carbon atom, and in addition, R-can also be structure (a),

R ¹²Be the replacement or the unsubstituted divalent alkyl of 2-3 carbon atom, its substituting group is the low alkyl group of one or more 1-4 carbon atom; Or replace or unsubstituted divalence 1,2-, 1,3-or 1,4-phenylene, its substituting group are low alkyl group, chlorine, bromine, nitro or the carboxyl of one or more 1-4 carbon atom, and,

R ⁶Be selected from: unsubstituted 4-12 carbon atom tertiary alkyl, 4-12 carbon atom tertiary alkyl of replacement, uncle's cycloalkyl of a 6-13 carbon atom, uncle's alkynyl of a 5-9 carbon atom and uncle's aralkyl of 9-13 carbon atom, wherein the substituting group of tertiary alkyl is the tertiary alkyl peroxy of 4-8 carbon atom.

2. as claimed in claim 1 pair (one-or two-excessively barkites), it is characterized in that it is selected from down group:

2,5-dimethyl-2,5-two (ethoxy carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (docosane oxygen base carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two [(4-tertiary butyl cyclohexyloxy) carbonyl carbonyl peroxy] hexane,

2,5-dimethyl-2,5-two (iso-borneol oxygen base carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (neopentyl oxygen carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (neopentyl oxygen carbonyl carbonyl peroxy)-3-hexin,

2,5-dimethyl-2,5-two (borneol oxygen base carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (benzyloxycarbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (tert-butoxycarbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (hexafluoro pentyloxy carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (chloro carbonyl carbonyl peroxy) hexane,

2,5-dimethyl-2,5-two (t-butylperoxy carbonyl carbonyl peroxy) hexane,

With 2,5-dimethyl-2,5-two (3-t-butylperoxy-1,3-dimethyl butoxy carbonyl carbonyl peroxy) hexane.

3. as claimed in claim 1 pair (one-or two-excessively barkites), it is characterized in that Q and Q ¹Identical, and R ¹, R ², R ³And R ⁴Identical and be the alkyl of 1-2 carbon atom.

4. as claimed in claim 3 pair (one-or two-excessively barkites), it is characterized in that Q and Q ¹Be selected from R-O and Cl.

5. as claimed in claim 4 pair (one-or two-excessively barkites), it is characterized in that Q and Q ¹Be R-O.

6. as claimed in claim 5 pair (one-or two-excessively barkites), it is characterized in that R ⁵Be selected from :-C ≡ C-and-(CH ₂) _n-, and n is 2.

7. as claimed in claim 6 pair (one-or two-excessively barkites), it is characterized in that R ⁵Be-(CH ₂) _n-, and n is 2.

8. as claimed in claim 7 pair (one-or two-excessively barkites), it is characterized in that R is selected from down group: H; The alkyl of a replacement or a unsubstituted 1-22 carbon atom, its substituting group is the alkyl of one or more 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, aryloxy, chlorine, bromine, carboxyl and the cyano group of a 6-10 carbon atom; The cycloalkyl of a replacement or a unsubstituted 5-12 carbon atom, its substituting group is the low alkyl group of one or more 1-4 carbon atom; 6-14 carbon atom replaces or unsubstituted bicyclic alkyl, and its substituting group is the low alkyl group of one or more 1-4 carbon atom; And structure (a).

One kind with claim 1 described two (-or two-cross barkites) compound as radical initiator cure unsaturated polyester resins method for compositions, it is characterized in that, under proper temperature and in the presence of the novel peroxide compound of the claim 1 of initiation amount, heat this resin.

10. method as claimed in claim 9 is characterized in that, this pair (crosses barkite) compound is 2,5-dimethyl-2,5-two (iso-borneol oxygen base carbonyl carbonyl peroxy) hexane.

11. one kind with the method for claim 1 described two (-or two-cross barkites) compound as radical initiator polymerization ethylenically unsaturated monomer, it is characterized in that, uses the novel peroxide compound of the claim 1 of initiation amount under proper temperature.

12. method as claimed in claim 8 is characterized in that, this ethylenically unsaturated monomer is a vinylchlorid.