CN110028653A - A kind of preparation method of high fire-retardance vinylite - Google Patents
A kind of preparation method of high fire-retardance vinylite Download PDFInfo
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- CN110028653A CN110028653A CN201910349159.7A CN201910349159A CN110028653A CN 110028653 A CN110028653 A CN 110028653A CN 201910349159 A CN201910349159 A CN 201910349159A CN 110028653 A CN110028653 A CN 110028653A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of preparation methods of high fire-retardance vinylite, the following steps are included: the first step is reacted: epoxy resin, tetrabromobisphenol A and catalyst are added in reaction kettle, it is warming up to single step reaction temperature after being stirred, reaches single step reaction terminal after keeping isothermal reaction to a certain amount of epoxide equivalent value；Second step reaction: suitable styrene is added, stirs evenly, when temperature drops to two step reaction temperatures, methacrylic acid is added, it stirs evenly, after entire reaction system is from heat release stabilization, adds catalyst and the reaction of two step reaction temperatures is kept to reach two step reaction ends；It adjusts dilution: suitable styrene is added and is diluted, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.The present invention provides one kind under the premise of guaranteeing product quality, reduces reaction mass in the viscosity of second stage, reduces stirring motor load, increase the preparation method of the vinylite using the time.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of preparation method of high fire-retardance vinylite.
Background technique
Vinyl ester resin is that vinyl group is contained in molecule end, and intermediate skeleton is that one kind of epoxy resin structural is special not
Saturated polyester resin usually react by esterification by ring opening with unsaturated monoacid by epoxy resin and is made, have concurrently epoxy with
The characteristics of two kinds of thermosetting resins of unsaturated polyester (UP)；Vinyl ester resin remains the basic segment of epoxy resin, and has insatiable hunger
With the good process performance of polyester resin, after can solidifying under optimum conditions, certain special excellent performances are shown, it is such as excellent
Mechanical performance, heat resistance and chemical resistance.
Existing production high fire-retardance vinylite is usually using epoxy resin, tetrabromobisphenol A, styrene and other small powders
Polymerization reaction is carried out, tetrabromobisphenol A is the derivative of bisphenol-A, is white powder, is mainly used as plastic products additive, is normal
The content of one of brominated flame retardant, tetrabromobisphenol A directly affects the anti-flammability of vinylite, but due to tetrabromobisphenol A
Molecular weight it is big, viscosity is high when melting, if the excessive material viscosity being easy to cause in reactor of additional amount increases, viscosity
It is uneven that increase will lead to material stirring in reactor, and local heating is unevenly easy gel, and the quality of product cannot ensure；
Since viscosity is too big, it will increase the load of stirring motor, motor be easy to cause to burn, but if increased tetrabromobisphenol A content
Vinyl ester resin poor fire that is small, then producing, is not achieved flame-retardancy requirements, is able to solve it is therefore desirable to find one kind
The method of the above problem.
Summary of the invention
It is an object of the invention to: in view of the above problems, one kind is provided under the premise of guaranteeing product quality,
Reaction mass is reduced in the viscosity of second stage, stirring motor load is reduced, increases the preparation of the vinylite using the time
Method.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of preparation method of high fire-retardance vinylite, comprising the following steps:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, after being stirred
It is warming up to single step reaction temperature, reaches single step reaction terminal after keeping isothermal reaction to a certain amount of epoxide equivalent value；
(2) second step reacts: the system that first step reaction is completed in step (1) is cooled down, be added suitable styrene and
Polymerization inhibitor stirs evenly, and when temperature drops to two step reaction temperatures, methacrylic acid is added, stirs evenly, when entire reaction
System from heat release stablize after, add the second catalyst keep two step reaction temperatures reaction reach two step reaction ends；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted,
Polymerization inhibitor is added again simultaneously, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
Further, the mass fraction of each raw material in the preparation method is as follows: 2500-3500 parts of epoxy resin, four
1800-2600 parts of bromine bisphenol-A, 5-15 parts of the first catalyst, 600-700 parts of methacrylic acid, 5-15 parts of the second catalyst, polymerization inhibitor
0.5-5 parts of agent, the styrene mass fraction being added in second step reaction is 800-900 parts, the benzene being added in adjusting dilution
Ethylene mass number is 3000-3500 parts.
Further, first catalyst is tetramethyl ammonium chloride, and second catalyst is triphenyl phosphorus, the resistance
Poly- agent is PHQ.
Further, in step (1), the single step reaction temperature is 125-165 DEG C, when keeping the reaction of isothermal reaction
Between be 30-60min, a certain amount of epoxide equivalent value be 400-500 grams/equivalent.Further, described in step (2)
It is the addition when the temperature of reaction system drops to 130 DEG C or less that styrene, which is added, and the two steps reaction temperature is 90-115 DEG C.
Further, the two steps reaction end is acid value less than 12, and epoxide equivalent value is 5000-12000 grams/equivalent.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
(1) preparation method in the present invention increases four to guarantee the flame retardant property of the vinylite prepared
The ratio of bromine bisphenol-A, while the material viscosity entirely reacted is reduced by the way that styrene dilution is added, to reduce stirring motor
Load increases its service life；
(2) after progress epoxy resin and tetrabromobisphenol A are carried out polymerization reaction in first step reaction by the present invention, due to viscous
Degree increases rapidly, and stirring is difficult, can not be successfully and is reacted with methacrylic acid, is cooled to 130 DEG C and styrene is once added afterwards
Dilution adds methacrylic acid reaction after reducing system viscosity, can guarantee the progress of subsequent esterification；
(3) methacrylic acid is added after temperature being reduced to 90-115 DEG C after addition styrene diluted system in the present invention
It is reacted, autohemagglutination phenomenon occurs when can be more than 120 DEG C to avoid methacrylic acid；(4) entire preparation method operating procedure letter
It is single, implement convenient for operation, and the vinylite excellent fireproof performance produced, can be widely popularized.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, preferred embodiment is enumerated below, to this hair
Bright further description.However, it is necessary to illustrate, many details listed in specification are used for the purpose of making reader to this
The one or more aspects of invention have a thorough explanation, also may be implemented even without these specific details of the invention
These aspects.
Embodiment 1
A kind of preparation method of high fire-retardance vinylite, comprising the following steps:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, after being stirred
It is warming up to 125 DEG C of single step reaction temperature, the epoxide equivalent value of isothermal reaction 30min extremely is kept to reach 400 grams/equivalent, reach the
Single step reaction terminal；
(2) second step reacts: the system that first step reaction is completed in step (1) is cooled to 130 DEG C hereinafter, benzene second is added
It 800 parts and 0.5 part of polymerization inhibitor of alkene, stirs evenly, when temperature drops to 90 DEG C of two step reaction temperatures, methacrylic acid is added,
It stirs evenly, after entire reaction system is from heat release stabilization, adds the second catalyst and the reaction of two step reaction temperatures is kept to reach
To two step reaction ends, two step reaction ends are acid value less than 12, and epoxide equivalent value is 5000 grams/equivalent；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted,
Polymerization inhibitor is added again simultaneously, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
Wherein the mass fraction of each raw material is as follows: 2500 parts of epoxy resin, 1800 parts of tetrabromobisphenol A, the first catalyst 5
Part, 600 parts of methacrylic acid, 5 parts of the second catalyst, 0.5 part of polymerization inhibitor, the styrene mass parts being added in second step reaction
Number is 800 parts, and the styrene mass fraction being added in adjusting dilution is 3000 parts, wherein the first catalyst is tetramethyl chlorination
Ammonium, second catalyst are triphenyl phosphorus, and the polymerization inhibitor is PHQ.
Embodiment 2
A kind of preparation method of high fire-retardance vinylite, comprising the following steps:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, after being stirred
It is warming up to 165 DEG C of single step reaction temperature, the epoxide equivalent value of isothermal reaction 60min extremely is kept to reach 500 grams/equivalent, reach the
Single step reaction terminal；
(2) second step reacts: the system that first step reaction is completed in step (1) is cooled to 130 DEG C hereinafter, benzene second is added
It 900 parts and 1 part of polymerization inhibitor of alkene, stirs evenly, when temperature drops to 115 DEG C of two step reaction temperatures, methacrylic acid is added, stirs
It mixes uniformly, after entire reaction system is from heat release stabilization, adds the second catalyst and the reaction of two step reaction temperatures is kept to reach
Two step reaction ends, two step reaction ends are acid value less than 12, and epoxide equivalent value is 12000 grams/equivalent；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted,
Polymerization inhibitor is added again simultaneously, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
Wherein the mass fraction of each raw material is as follows: 3500 parts of epoxy resin, 2600 parts of tetrabromobisphenol A, the first catalyst 15
Part, 700 parts of methacrylic acid, 15 parts of the second catalyst, 5 parts of polymerization inhibitor, the styrene mass parts being added in second step reaction
Number is 900 parts, and the styrene mass fraction being added in adjusting dilution is 3500 parts, wherein the first catalyst is tetramethyl chlorination
Ammonium, second catalyst are triphenyl phosphorus, and the polymerization inhibitor is PHQ.
Embodiment 3
A kind of preparation method of high fire-retardance vinylite, comprising the following steps:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, after being stirred
It is warming up to 125 DEG C of single step reaction temperature, the epoxide equivalent value of isothermal reaction 45min extremely is kept to reach 450 grams/equivalent, reach the
Single step reaction terminal；
(2) second step reacts: the system that first step reaction is completed in step (1) is cooled to 130 DEG C hereinafter, benzene second is added
It 850 parts and 0.8 part of polymerization inhibitor of alkene, stirs evenly, when temperature drops to 105 DEG C of two step reaction temperatures, methacrylic acid is added,
It stirs evenly, after entire reaction system is from heat release stabilization, adds the second catalyst and the reaction of two step reaction temperatures is kept to reach
To two step reaction ends, two step reaction ends are acid value less than 12, and epoxide equivalent value is 9000 grams/equivalent；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted,
Polymerization inhibitor is added again simultaneously, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
Wherein the mass fraction of each raw material is as follows: 3000 parts of epoxy resin, 2200 parts of tetrabromobisphenol A, the first catalyst 10
Part, 650 parts of methacrylic acid, 10 parts of the second catalyst, 2 parts of polymerization inhibitor, the styrene mass parts being added in second step reaction
Number is 850 parts, and the styrene mass fraction being added in adjusting dilution is 3250 parts, wherein the first catalyst is tetramethyl chlorination
Ammonium, second catalyst are triphenyl phosphorus, and the polymerization inhibitor is PHQ.
Embodiment 4
A kind of preparation method of high fire-retardance vinylite, comprising the following steps:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, after being stirred
It is warming up to 140 DEG C of single step reaction temperature, the epoxide equivalent value of isothermal reaction 40min extremely is kept to reach 420 grams/equivalent, reach the
Single step reaction terminal；
(2) second step reacts: the system that first step reaction is completed in step (1) is cooled to 130 DEG C hereinafter, benzene second is added
It 825 parts and 0.6 part of polymerization inhibitor of alkene, stirs evenly, when temperature drops to 100 DEG C of two step reaction temperatures, methacrylic acid is added,
It stirs evenly, after entire reaction system is from heat release stabilization, adds the second catalyst and the reaction of two step reaction temperatures is kept to reach
To two step reaction ends, two step reaction ends are acid value less than 12, and epoxide equivalent value is 6000 grams/equivalent；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted,
Polymerization inhibitor is added again simultaneously, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
Wherein the mass fraction of each raw material is as follows: 2800 parts of epoxy resin, 2000 parts of tetrabromobisphenol A, the first catalyst 8
Part, 640 parts of methacrylic acid, 9 parts of the second catalyst, 2 parts of polymerization inhibitor, the styrene mass fraction being added in second step reaction
It is 800-900 parts, the styrene mass fraction being added in adjusting dilution is 3200 parts, wherein the first catalyst is tetramethyl chlorine
Change ammonium, second catalyst is triphenyl phosphorus, and the polymerization inhibitor is PHQ.
Embodiment 5
A kind of preparation method of high fire-retardance vinylite, comprising the following steps:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, after being stirred
It is warming up to 150 DEG C of single step reaction temperature, the epoxide equivalent value of isothermal reaction 50min extremely is kept to reach 480 grams/equivalent, reach the
Single step reaction terminal；
(2) second step reacts: the system that first step reaction is completed in step (1) is cooled to 130 DEG C hereinafter, benzene second is added
It 880 parts and 0.9 part of polymerization inhibitor of alkene, stirs evenly, when temperature drops to 110 DEG C of two step reaction temperatures, methacrylic acid is added,
It stirs evenly, after entire reaction system is from heat release stabilization, adds the second catalyst and the reaction of two step reaction temperatures is kept to reach
To two step reaction ends, two step reaction ends are acid value less than 12, and epoxide equivalent value is 10000 grams/equivalent；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted,
Polymerization inhibitor is added again simultaneously, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
Wherein the mass fraction of each raw material is as follows: 3000 parts of epoxy resin, 2300 parts of tetrabromobisphenol A, the first catalyst 12
Part, 670 parts of methacrylic acid, 12 parts of the second catalyst, 3 parts of polymerization inhibitor, the styrene mass parts being added in second step reaction
Number is 890 parts, and the styrene mass fraction being added in adjusting dilution is 3400 parts, wherein the first catalyst is tetramethyl chlorination
Ammonium, the second catalyst are triphenyl phosphorus, polymerization inhibitor PHQ.
The vinylite prepared in above embodiments 1- embodiment 5 is subjected to viscosity test viscosity respectively, due to temperature
Greater than 130 DEG C, with unsaturated double-bond group violent cross-linked polymeric can occur for styrene, lead to gel.Temperature is greater than 125 DEG C
When, autohemagglutination can occur for methacrylic acid, lead to gel, thus when temperature drops to 125 DEG C after first step reaction end also into
The viscosity that row viscosity test is surveyed is denoted as η0, tested viscosity is η second step adds styrene when reacting after1, then every reaction one
Viscosity of hour test is denoted as η respectively2、η3、η4、η5, and when temperature drops to 125 DEG C after first step reaction end also into
The viscosity that row viscosity test is surveyed is denoted as η0, the use of viscosity test instrument brand is U.S. brookfield, model in experiment
CAP2000+, viscosimeter type are vertebral plate viscosimeter, and test scope is 0.2-375 (MPa.s), and sample heating device is H series
(50-235 DEG C) uses viscosimeter test parameter: at 125 DEG C, No. 3 rotors, and 750 turns, wherein the data tested such as following table institute
Show:
| η0/p | η1/p | η2/p | η3/p | η4/p | η5/p | |
| Embodiment 1 | 4.89 | 1.79 | 2.14 | 2.51 | 3.15 | 3.93 |
| Embodiment 2 | 4.96 | 1.83 | 2.10 | 2.53 | 3.10 | 3.87 |
| Embodiment 3 | 4.92 | 1.82 | 2.13 | 2.54 | 3.11 | 3.89 |
| Embodiment 4 | 4.91 | 1.80 | 2.16 | 2.50 | 3.17 | 3.91 |
| Embodiment 5 | 4.99 | 1.84 | 2.20 | 2.55 | 3.19 | 3.95 |
As seen from the above table, after styrene being added in second step reaction, the viscosity fall of entire reaction system is big,
In the esterification reaction process of second step reaction, viscosity slowly rises, and guarantees that entirely reacts goes on smoothly, after the completion of end reaction
Addition styrene is diluted to obtain high fire-retardance vinylite finished product.Preparation method of the invention can make tetrabromo in formula
It can guarantee going on smoothly for reaction in the higher situation of the content of bisphenol-A, prepare the vinyl tree with high flame resistance
Rouge.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of high fire-retardance vinylite, it is characterised in that: the following steps are included:
(1) first step is reacted: epoxy resin, tetrabromobisphenol A and the first catalyst being added in reaction kettle, heated up after being stirred
To single step reaction temperature, reach single step reaction terminal after keeping isothermal reaction to a certain amount of epoxide equivalent value；
(2) second step reacts: the system for completing first step reaction in step (1) being cooled down, suitable styrene and polymerization inhibitor is added
Agent stirs evenly, and when temperature drops to two step reaction temperatures, methacrylic acid is added, stirs evenly, when entire reaction system
From heat release stablize after, add the second catalyst keep two step reaction temperatures reaction reach two step reaction ends；
(3) it adjusts dilution: suitable styrene is added to the system for completing second step reaction in step (2) and is diluted, simultaneously
Polymerization inhibitor is added again, and is cooled to room temperature after mixing evenly, obtains high fire-retardance vinylite finished product.
2. a kind of preparation method of high fire-retardance vinylite according to claim 1, it is characterised in that: the preparation side
The mass fraction of each raw material in method is as follows: 2500-3500 parts of epoxy resin, 1800-2600 parts of tetrabromobisphenol A, the first catalysis
5-15 parts of agent, 600-700 parts of methacrylic acid, 5-15 parts of the second catalyst, 0.5-5 parts of polymerization inhibitor add in second step reaction
The styrene mass fraction entered is 800-900 parts, and the styrene mass fraction being added in adjusting dilution is 3000-3500 parts.
3. a kind of preparation method of high fire-retardance vinylite according to claim 2, it is characterised in that: described first urges
Agent is tetramethyl ammonium chloride, and second catalyst is triphenyl phosphorus, and the polymerization inhibitor is PHQ.
4. a kind of preparation method of high fire-retardance vinylite according to claim 3, it is characterised in that: in step (1)
In, the single step reaction temperature is 125-165 DEG C, and being kept for the reaction time of isothermal reaction is 30-60min, described a certain amount of
Epoxide equivalent value is 400-500 grams/equivalent.
5. a kind of preparation method of high fire-retardance vinylite according to claim 3, it is characterised in that: in step (2)
In, the addition styrene is the addition when the temperature of reaction system drops to 130 DEG C or less, and the two steps reaction temperature is
90-115℃。
6. a kind of preparation method of high fire-retardance vinylite according to claim 5, it is characterised in that: two step is anti-
Answering terminal is acid value less than 12, and epoxide equivalent value is 5000-12000 grams/equivalent.
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Application publication date: 20190719 |