CN106188499B - A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer - Google Patents

A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer Download PDF

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CN106188499B
CN106188499B CN201610557528.8A CN201610557528A CN106188499B CN 106188499 B CN106188499 B CN 106188499B CN 201610557528 A CN201610557528 A CN 201610557528A CN 106188499 B CN106188499 B CN 106188499B
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China
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castor oil
base
flame retardant
vinyl ester
retardant type
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CN201610557528.8A
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Chinese (zh)
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CN106188499A (en
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夏建陵
李守海
毛伟
黄坤
李梅
杨雪娟
宋健
许利娜
杨小华
张燕
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中国林业科学研究院林产化学工业研究所
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Abstract

A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer, castor oil-base epoxy resin is made in castor oil acid and epichlorohydrin reaction, then flame retardant type castor oil-base phosphate is made through epoxy ring opening reaction in castor oil-base epoxy resin and phosphate, flame retardant type castor oil-base vinyl ester resin monomer is finally made with unsaturated acids anhydride reactant.Flame retardant type bio-based vinyl ester resin is prepared by raw material of castor oil, its anti-flammability is controllable, iodine number is high, and obtained product is in terms of anti-flammability and weatherability being expected to improve the shortcomings that traditional unsaturated-resin is in these two aspects, and the comprehensive performance of vinylite solidfied material is improved at the same time.Preparation process is simple, and condition compares mitigation, uses cheap reproducible vegetable fat to prepare the vinyl ester resin of high added value for raw material, while extend its application in high temperature area.

Description

A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer

Technical field

The invention belongs to unsaturated-resin field, more particularly to a kind of flame retardant type castor oil-base vinyl ester resin monomer Preparation method.

Background technology

The vinyl ester resin monomer reacted by unsaturated carboxylic acid and epoxy resin is thermoset copolymer and insatiable hunger Represented with one kind of polyester.The solidfied material of vinyl ester resin has good mechanical property, higher chemical stability and resistance to The advantages that hot, be widely used in petrochemical industry, space flight and aviation, plating, building, food, medicine and other fields.

The raw material of currently used vinyl ester resin monomer is greatly mostly from petrochemical materials, therefore the resin list synthesized Then containing many rigid benzene ring structures in body so that brittleness is larger after hardening for resin monomer.Therefore at present frequently with flexible life Thing based raw material improves its toughness to prepare vinyl ester resin monomer.Poor fire, which but becomes, at the same time hinders vinyl ester resin An important factor for monomer further develops.At present, the flame resistant method of vinyl ester resin monomer mainly has addition type and response type Fire-retardant two methods.Generally use latter flame resistant method, because additive flame burning method can cause curing system, there are fire-retardant Phenomena such as performance is low, fire retardant easily separates out.In view of continuous improvement of the people to health understanding, halogen-free flame retardants especially phosphorus system hinders Combustion agent is developed rapidly.Phosphoric acid ester, can be anti-with the generation such as anhydride group, epoxy group and carboxyl because containing-OH in structure The derivative of a kind of high flame retardant, high stability should be formed, thus is received much concern.In addition, phosphorous vinyl ester resin monomer It is a kind of resin monomer of environmental type, will not damages in use to the body and environment of people.

In addition, environmental protection and the continuous of health perception are strengthened with economic fast development, and people, at the same time Fossil feedstock class product and middle product all have strong impulse taste, are unsuitable for people's Long Term Contact, therefore using inexpensive nontoxic Reproducible biology grease substitutes the non-renewable petroleum to be current being badly in need of completing of the task.

A kind of new flame-retardant vinyl ester resin monomer is prepared using biological grease, not only increases epoxy resin The fire resistance of material, also so that non-edible vegetable oil fat is anticipated in high-valued industry development using upper with important research Justice.

Castor oil is China the most common type oil crops, is widely distributed in the ground such as China northeast, North China, annual output position Rank the third of the world, because of its abundance, therefore in the field such as coating, plastics, polyurethane and rubber extensive application.In castor oil Containing a large amount of carboxyls, ester group and double bond, can occur a variety of chemical reactions, such as ester exchange, dehydration, and pyrolysis, epoxidation, esterification are anti- Should, addition reaction etc..Therefore new active group and final is introduced by epoxidation reaction using the castor oil acid containing carboxyl Flame retardant type castor oil-base vinyl ester resin monomer is made.Develop environmentally friendly, safe and energy saving flame retardant type bio-based vinyl esters Resin is one of Main way of future development.

The content of the invention

The technical problem of solution:Traditional vinyl ester resin there are poor fire, toxic component content is high the shortcomings of, be Improving its shortcoming, fire retardant is incorporated into vinyl ester resin monomer by the present invention, to strengthen the anti-flammability of vinyl ester resin, A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer is devised, the preparation of phosphor-containing flame-proof monomer, is expected to carry The anti-flammability of high-vinyl ester resin.Reaction condition is gentle in the synthesis process for this method, and obtained product stability is good.

Technical solution:A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer, is made by following steps: Castor oil acid is added in reaction vessel, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio adds ring Oxygen chloropropane, adds the benzyltriethylammoinium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reaction 2h;Cooling To 60 DEG C, calcium oxide and sodium hydroxide with carboxyl equimolar number are added, 3h is stirred at 60 DEG C;Most afterwards through filtering, revolving removes Castor oil-base epoxy resin is made in unnecessary epoxychloropropane;By castor oil-base epoxy resin and account for reactant gross mass 0.5~1.5% catalyst A is added in reactor, is warming up to 40~50 DEG C, and phosphate, the phosphoric acid then is added dropwise to it The molar ratio of ester and castor oil-base epoxy resin is 1~1.2:1, after being added dropwise, 70~80 DEG C of 3~5h of reaction, are made fire-retardant Type castor oil-base phosphate;Then by castor oil-base phosphate and unsaturated acid anhydride according to molar ratio 1:2~2.1 ratio adds Into reaction vessel, the polymerization inhibitor for the catalyst B and 0.1~0.25% for accounting for reactant gross mass 0.5~1.5% is added, through weak Alkali cleaning and revolving obtain flame retardant type castor oil-base vinyl ester resin monomer.

Above-mentioned phosphate is dibutylphosphoric acid ester or diethyl phosphate.

Above-mentioned unsaturated acid anhydride is methacrylic anhydride, itaconic anhydride or maleic anhydride.

Above-mentioned catalyst A is triphenylphosphine, N, N dimethyl benzylamine or cetyl trimethylammonium bromide.

Above-mentioned catalyst B is tetraethylammonium bromide, benzyltrimethylammonium chloride or 4 bromide.

Above-mentioned polymerization inhibitor is hydroquinone or di-tert-butyl hydroquinone.

Beneficial effect:1) flame retardant type bio-based vinyl ester resin is prepared by raw material of castor oil, its anti-flammability is controllable, iodine Value is high, and obtained product in terms of the anti-flammability and weatherability on be expected to improve traditional unsaturated-resin in these two aspects Shortcoming, and the comprehensive performance of vinylite solidfied material is improved at the same time.2) phosphor-containing flame-proof intermediate is incorporated into vinyl esters In resin, solves the problems, such as vinyl ester resin poor fire in use, this is conducive to extend vinyl ester resin Application in high temperature Flammable atmosphere, while phosphorous flame-retardant vinyl ester resin material in use will not be to the body of people Body and environmental pollution.3) crude vegetal castor oil is used as raw material, by simply hydrolyzing, being esterified, epoxy addition etc. Reaction obtains flame-retardant vinyl ester resin, and raw material sources enrich, and preparation process is simple, not only save the consumption of the energy, and And it is environmentally friendly in the synthesis process, and slow down consuming excessively for petrochemical industry resource.

Brief description of the drawings

Fig. 1 is the infrared spectrum of flame retardant type castor oil-base vinyl ester resin monomer (MDDRA) and intermediate (DDRA) Figure;3379.2cm in DDRA-1Neighbouring absworption peak is the characteristic absorption peak of hydroxyl, 1738.9cm-1It is the characteristic peak of ester group, 1120 and 910cm-1It is the characteristic peak of P-O-C, 1030cm-1Left and right is the characteristic peak of P-O, 1245cm-1Place is that the feature of P=O is inhaled Receipts peak, and 856cm-1The characteristic absorption peak for locating epoxy group disappears, and illustrates that the hydroxyl of epoxy group and phosphate reacts;MDDRA Infrared spectrum in 1785 and 1636cm-1There is new C=O and C=C in place, illustrates that methacrylic anhydride occurs with DDRA Reaction.

Embodiment

Certain embodiments are given below so that the present invention will be further described, but following embodiments are not that the present invention is protected The limitation explanation of scope, field technology personnel according to the present invention make some nonessential modifications and adaptations and still belong to this hair by content Bright protection content.

Embodiment 1

Castor oil acid is added in reaction vessel, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio Example adds epoxychloropropane, adds the benzyltriethylammoinium chloride of above-mentioned reaction raw materials gross mass 1.0wt%, 115 DEG C of reactions 2h;60 DEG C are cooled to, calcium oxide and sodium hydroxide with carboxyl equimolar number is added, 3h is stirred at 60 DEG C.Most afterwards through filtering, rotation Unnecessary epoxychloropropane is evaporated off castor oil-base epoxy resin is made.By castor oil-base epoxy resin and account for the total matter of reactant The triphenylphosphine of amount 0.5wt% is added in reaction vessel, is warming up to 40 DEG C, and dibutylphosphoric acid ester, di(2-ethylhexyl)phosphate then is added dropwise to it The molar ratio of butyl ester and castor oil-base epoxy resin is 1:1, after being added dropwise, 70 DEG C of reaction 3h, are made flame retardant type castor oil-base Phosphate.Then by castor oil-base phosphate and methacrylic anhydride according to molar ratio 1:2 ratio is added in reaction vessel, The hydroquinone of the tetraethylammonium bromide and 0.1wt.% that account for reactant gross mass 0.5wt.% is added, washes and rotates through weak base To flame retardant type castor oil-base vinyl ester resin monomer.

Embodiment 2

Castor oil acid is added in reaction vessel, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio Example adds epoxychloropropane, adds the benzyl triethyl ammonium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reactions 2h;60 DEG C are cooled to, calcium oxide and sodium hydroxide with carboxyl equimolar number is added, 3h is stirred at 60 DEG C.Most afterwards through filtering, rotation Unnecessary epoxychloropropane is evaporated off castor oil-base epoxy resin is made.By castor oil-base epoxy resin and account for the total matter of reactant The N of amount 0.8%, N dimethyl benzylamine are added in reaction vessel, are warming up to 50 DEG C, and diethyl phosphate, castor-oil plant then is added dropwise to it The molar ratio of oil base epoxy resin and diethyl phosphate is 1.2:1, after being added dropwise, 80 DEG C of reaction 5h, are made flame retardant type castor-oil plant Oil base phosphate.Then by castor oil-base phosphate and itaconic anhydride according to molar ratio 1:2.1 ratio is added to reaction vessel In, the hydroquinone of the benzyltrimethylammonium chloride and 0.25wt.% that account for reactant gross mass 1.5wt.% is added, is washed through weak base And revolving obtains flame retardant type castor oil-base vinyl ester resin monomer.

Embodiment 3

Castor oil acid is added in reaction vessel, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio Example adds epoxychloropropane, adds the benzyltriethylammoinium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reactions 2h;60 DEG C are cooled to, calcium oxide and sodium hydroxide with carboxyl equimolar number is added, 3h is stirred at 60 DEG C.Most afterwards through filtering, rotation Unnecessary epoxychloropropane is evaporated off castor oil-base epoxy resin is made.By castor oil-base epoxy resin and account for the total matter of reactant The cetyl trimethylammonium bromide of the 1.0wt.% of amount is added in reaction vessel, is warming up to 45 DEG C, and phosphorus then is added dropwise to it The molar ratio of dibutyl phthalate, castor oil-base epoxy resin and dibutylphosphoric acid ester is 1.1:1, after being added dropwise, 75 DEG C of reaction 4h, system Obtain flame retardant type castor oil-base phosphate.Then by castor oil-base phosphate and maleic anhydride according to molar ratio 1:2.05 ratio adds Enter into reaction vessel, add the di-t-butyl pair of the 4 bromide and 0.2wt.% that account for reactant gross mass 1.0wt.% Benzenediol, washes and rotates through weak base and obtain flame retardant type castor oil-base vinyl ester resin monomer.

Embodiment 4

Castor oil acid is added in reactor, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio Epoxychloropropane is added, adds the benzyltriethylammoinium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reactions 2h;60 DEG C are cooled to, calcium oxide and sodium hydroxide with carboxyl equimolar number is added, 3h is stirred at 60 DEG C.Most afterwards through filtering, rotation Unnecessary epoxychloropropane is evaporated off castor oil-base epoxy resin is made.By castor oil-base epoxy resin and account for the total matter of reactant The triphenylphosphine of the 1.2wt.% of amount is added in reaction vessel, is warming up to 48 DEG C, and diethyl phosphate, castor-oil plant then is added dropwise to it The molar ratio of oil base epoxy resin and diethyl phosphate is 1.1:1, after being added dropwise, 78 DEG C of reaction 5h, are made flame retardant type castor-oil plant Oil base phosphate.Then by castor oil-base phosphate and methacrylic anhydride according to molar ratio 1:2.1 ratio is added to reaction In container, addition accounts for the benzyltrimethylammonium chloride of reactant gross mass 1.2wt.% and the di-t-butyl of 0.2wt.% to benzene two Phenol, washes and rotates through weak base and obtain flame retardant type castor oil-base vinyl ester resin monomer.

Embodiment 5

Castor oil acid is added in reaction vessel, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio Example adds epoxychloropropane, adds the benzyl triethyl ammonium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reactions 2h;60 DEG C are cooled to, calcium oxide and sodium hydroxide with carboxyl equimolar number is added, 3h is stirred at 60 DEG C.Most afterwards through filtering, rotation Unnecessary epoxychloropropane is evaporated off castor oil-base epoxy resin is made.By castor oil-base epoxy resin and account for the total matter of reactant The N of the 0.8wt.% of amount, N dimethyl benzylamine are added in reaction vessel, are warming up to 45 DEG C, and di(2-ethylhexyl)phosphate fourth then is added dropwise to it The molar ratio of ester, castor oil-base epoxy resin and dibutylphosphoric acid ester is 1:1, after being added dropwise, 75 DEG C of reaction 4.5h, are made fire-retardant Type castor oil-base phosphate.Then by castor oil-base phosphate and maleic anhydride according to molar ratio 1:2 ratio is added to reaction In container, the hydroquinone of the 4 bromide and 0.15wt.% that account for reactant gross mass 0.8wt.% is added, is washed through weak base And revolving obtains flame retardant type castor oil-base vinyl ester resin monomer.

Embodiment 6

Castor oil acid is added in reactor, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio Epoxychloropropane is added, adds the benzyltriethylammoinium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reactions 2h;60 DEG C are cooled to, calcium oxide and sodium hydroxide with carboxyl equimolar number is added, 3h is stirred at 60 DEG C.Most afterwards through filtering, rotation Unnecessary epoxychloropropane is evaporated off castor oil-base epoxy resin is made.By castor oil-base epoxy resin and account for the total matter of reactant The cetyl trimethylammonium bromide of the 0.6wt.% of amount is added in reaction vessel, is warming up to 46 DEG C, and phosphorus then is added dropwise to it The molar ratio of diethyl phthalate, castor oil-base epoxy resin and diethyl phosphate is 1.2:1, after being added dropwise, 78 DEG C of reaction 4.5h, Flame retardant type castor oil-base phosphate is made.Then by castor oil-base phosphate and itaconic anhydride according to molar ratio 1:2.1 ratio It is added in reaction vessel, adds two tertiary fourths of the tetraethylammonium bromide and 0.18wt.% that account for reactant gross mass 1.2wt.% Base hydroquinone, washes and rotates through weak base and obtain flame retardant type castor oil-base vinyl ester resin monomer.

Comparative example:

Experimental group 1:Flame retardant type castor oil-base vinyl ester resin monomer prepared by embodiment 1 is accurately weighed into 20g, then Polyethylene glycol dimethacrylate 10g is added, adds 1.5% initiator benzoyl peroxide and 0.5% cobalt naphthenate, is mixed Conjunction is uniformly placed in the mould of special requirement, and precuring 3h, resolidification after being then increased to 160 DEG C again are heated at 120 DEG C 4h, then slow cooling to room temperature is the copolymeric material being made after curing.

Experimental group 2:Flame retardant type castor oil-base vinyl ester resin monomer prepared by embodiment 2 is accurately weighed into 20g, then Polyethylene glycol dimethacrylate 10g is added, adds 1.5% initiator benzoyl peroxide and 0.5% cobalt naphthenate, is mixed Conjunction is uniformly placed in the mould of special requirement, and precuring 3h, resolidification after being then increased to 160 DEG C again are heated at 120 DEG C 4h, then slow cooling to room temperature is the copolymeric material being made after curing.

Experimental group 3:Flame retardant type castor oil-base vinyl ester resin monomer prepared by embodiment 3 is accurately weighed into 20g, then Polyethylene glycol dimethacrylate 10g is added, adds 1.5% initiator benzoyl peroxide and 0.5% cobalt naphthenate, is mixed Conjunction is uniformly placed in the mould of special requirement, and precuring 3h, resolidification after being then increased to 160 DEG C again are heated at 120 DEG C 4h, then slow cooling to room temperature is the copolymeric material being made after curing.

Experimental group 4:Flame retardant type castor oil-base vinyl ester resin monomer prepared by embodiment 4 is accurately weighed into 20g, then Polyethylene glycol dimethacrylate 10g is added, adds 1.5% initiator benzoyl peroxide and 0.5% cobalt naphthenate, is mixed Conjunction is uniformly placed in the mould of special requirement, and precuring 3h, resolidification after being then increased to 160 DEG C again are heated at 120 DEG C 4h, then slow cooling to room temperature is the copolymeric material being made after curing.

Comprehensive mechanical property is carried out to above two thermosetting material and fire resistance is analyzed, institute in measurement result such as table 1 State.

Table 1 takes the heat cure performance comparison of each experimental group at random

Project Hardness LOI/% Tensile strength/MPa Experimental group 1 2H 28.6 15.6 Experimental group 2 H 27.2 14.3 Experimental group 3 H 26.8 14.0 Experimental group 4 2H 26.6 14.2

Note:Cure batten hardness to test with reference to GB6739-1996, LOI is with reference to national standard GB/T 2406-2009, tensile property With reference to GB/T 1040.3-2006 plastic tensile test methods, using CMT4000 type microcomputer controlled electronic universal testers (Shenzhen Newly think carefully), the tensile property extension test speed for measuring material is 10mm/min, and test temperature is 25 DEG C.

Claims (4)

1. a kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer, it is characterised in that be made by following steps: Castor oil acid is added in reaction vessel, then according to castor oil acid and epoxychloropropane molar ratio 1:8 ratio adds ring Oxygen chloropropane, adds the benzyltriethylammoinium chloride of above-mentioned reaction raw materials gross mass 1.0wt.%, 115 DEG C of reaction 2h;It is cooled to 60 DEG C, calcium oxide and sodium hydroxide with carboxyl equimolar number are added, 3h is stirred at 60 DEG C;Most afterwards through filtering, revolving removes more Castor oil-base epoxy resin is made in remaining epoxychloropropane;By castor oil-base epoxy resin and account for reactant gross mass 0.5 ~ The catalyst A of 1.5 % is added in reactor, and the catalyst A is triphenylphosphine, N, N- dimethyl benzylamines or cetyl three Methyl bromide ammonium, is warming up to 40 ~ 50 DEG C, and phosphate then is added dropwise to it, and the phosphate rubs with castor oil-base epoxy resin You are than being 1 ~ 1.2:1, after being added dropwise, 70~80 DEG C of 3 ~ 5h of reaction, are made flame retardant type castor oil-base phosphate;Then by castor-oil plant Oil base phosphate and unsaturated acid anhydride are according to molar ratio 1:2 ~ 2.1 ratio is added in reaction vessel, and it is total that addition accounts for reactant The polymerization inhibitor of the catalyst B and 0.1 ~ 0.25% of 0.5 ~ 1.5 % of quality, the catalyst B is tetraethylammonium bromide, benzyl front three Ammonium chloride or 4 bromide, wash and rotate through weak base and obtain flame retardant type castor oil-base vinyl ester resin monomer.
2. a kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer according to claim 1, its feature It is dibutylphosphoric acid ester or diethyl phosphate to be the phosphate.
3. a kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer according to claim 1, its feature It is methacrylic anhydride, itaconic anhydride or maleic anhydride to be the unsaturated acid anhydride.
4. a kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer according to claim 1, its feature It is hydroquinone or di-tert-butyl hydroquinone to be the polymerization inhibitor.
CN201610557528.8A 2016-07-14 2016-07-14 A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer CN106188499B (en)

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US7524909B2 (en) * 2004-05-07 2009-04-28 Drexel University Fatty acid monomers to reduce emissions and toughen polymers
CN102826995B (en) * 2012-09-07 2014-08-13 中国林业科学研究院林产化学工业研究所 Low-viscosity turpentine-based monoterpene vinyl ester resin monomer and preparation method and application thereof
CN103641961B (en) * 2013-11-29 2017-01-11 浙江天和树脂有限公司 Low-cost halogen-free chemical flame-retardant vinyl ester resin and preparation method thereof
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CN104086426B (en) * 2014-07-10 2015-12-30 中国林业科学研究院林产化学工业研究所 The preparation method of myrcenyl vinyl ester resin monomer
CN104387564B (en) * 2014-11-04 2016-09-14 中国林业科学研究院林产化学工业研究所 The preparation method of flame retardant type Fructus Citri tangerinae quintessence oil base vinyl ester resin monomer

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