CN110128987A - A kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof - Google Patents

A kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof Download PDF

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CN110128987A
CN110128987A CN201910465937.9A CN201910465937A CN110128987A CN 110128987 A CN110128987 A CN 110128987A CN 201910465937 A CN201910465937 A CN 201910465937A CN 110128987 A CN110128987 A CN 110128987A
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parts
added
prepare
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张海东
陈永峰
孟胜国
张永生
张清华
李宗霖
王业飞
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Shanxi Engineering Institute
Shanxi Institute of Technology
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Shanxi Engineering Institute
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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of Anchor Agent high temperature resistant high tenacity resins and preparation method thereof, wherein raw material includes maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol etc., polymerization inhibitor can be used for preventing the progress of polymerization, inhibit agent molecule and chain radical reaction, the low activity free radical that forms non-free radical substance or cannot cause, to make polymerization；Linear polyester, with vinyl monomer crosslinking curing, forms the resin of netted body structure under initiator, promotor effect；Inorganic filler is added in the present invention in preparing resin raw material, realizes organic and inorganic doping, can effectively improve the intensity and toughness of resin；The components such as aluminium triphosphate, aluminium metaphosphate are generated using phosphoric acid, aluminium hydroxide reaction simultaneously, these components have preferable high temperature resistance, can effectively improve the high temperature resistance of resin, and each raw material component is at low cost, and it is economical and practical, there is preferable practicability.

Description

A kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof
Technical field
The present invention relates to Anchor Agent resin making technique field, specifically a kind of Anchor Agent high temperature resistant high tenacity resins And preparation method thereof.
Background technique
Anchoring is securely seated between metal bolts, deformed bar, riffled tube in concrete, rock datum hole and replaces pre-buried steel The method of muscle referred to as " anchors ".Anchoring process is generally divided into expansible anchor of metal method and chemical bonding method.Wherein chemical bonding anchor Gu metal rod and matrix are securely joined with into an entirety using with binder, binder used is known as resin anchor Gu agent, resin anchoring agent is generally made of Special Resin, high-strength filler, curing agent, promotor and various auxiliary agents.
Nowadays the general high temperature resistance of Anchor Agent resin, the toughness in market are poor, hold during actually anchoring Security risk easily is brought, our use is influenced, makes troubles to us.
For this problem, we devise a kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof, effectively The high temperature resistance of Anchor Agent resin is improved, this is our urgent problems to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of Anchor Agent high temperature resistant high tenacity resins and preparation method thereof, existing to solve There is the problems in technology.
To achieve the above object, the invention provides the following technical scheme:
A kind of Anchor Agent high temperature resistant high tenacity resin, the high tenacity resin each raw material component are as follows: by weight, suitable 20-40 parts of anhydride maleique, 5-15 parts of dicyclopentadiene, 5-10 parts of phthalic anhydride, 3-6 parts of propylene glycol, styrene 6-14 Part, 1-3 parts of polymerization inhibitor, 5-10 parts of binder, 12-18 parts of additive.
A kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof is devised in the present invention, wherein raw material includes suitable Anhydride maleique, dicyclopentadiene, phthalic anhydride, propylene glycol etc., polymerization inhibitor can be used for preventing the progress of polymerization, resistance Poly- agent molecule and chain radical reaction, the low activity free radical that forms non-free radical substance or cannot cause, to make polymerization eventually Only.
Optimally, the additive each raw material component is as follows: by weight, 80-100 parts of phosphoric acid, aluminium hydroxide 25-30 Part, 5-18 parts of glass fibre and 10-25 parts of filler.
Optimally, the filler each raw material component is as follows: by weight, 15-20 parts of aluminium oxide, silica 6-14 Part, 1-5 parts of magnesia, 3-5 parts of modifying agent.
Optimally, the binder each raw material component is as follows: by weight, 10-15 parts of polyvinyl alcohol, 4-8 parts of gelatin With 1-2 parts of terephthalaldehyde.
Optimally, the polymerization inhibitor is hydroquinone；The modifying agent is Silane coupling reagent KH-570.
Optimally, the preparation method of a kind of Anchor Agent high temperature resistant high tenacity resin, comprising the following steps:
1) prepare material:
2) phosphoric acid for taking step 1) to prepare, is configured to phosphoric acid solution, and the hydrogen that step 1) prepares is added in heating heating in batches Aluminium oxide, stirring, constant-temperature condensation reflux obtain first material；
3) first material for taking step 2) to prepare, drying grinding, is sintered 3-3.5h, obtains second material；
4) 2/3 maleic anhydride for taking step 1) to prepare, heating heating, blender stirring are continuously heating to, slowly drip The dicyclopentadiene for adding step 1) to prepare, reaction, then phthalic anhydride is added, propylene glycol is added batch-wise, is added after reaction surplus Under 1/3 maleic anhydride, reaction a period of time, be cooled to 170-180 DEG C after reaction was completed, polymerization inhibitor be added, is cooled to Styrene is added at 120-130 DEG C, stirs evenly, obtains third material；
5) polyvinyl alcohol, the gelatin for taking step 1) to prepare are mixed polyvinyl alcohol, gelatin using deionized water, stand Swelling, rising temperature for dissolving are added terephthalaldehyde, are stirred to react, and stand, and filter, and wash, dry, obtain 4 materials；
6) 4 materials prepared by second material, the third material of step 4) preparation, the step 5) for taking step 3) to prepare, are mixed It closes uniformly, sequentially adds aluminium oxide, silica, magnesium dioxide and modifying agent, heating stirring adds glass fibre, surpasses Sound dispersion, it is cooling, obtain finished product.
Optimally, comprising the following steps:
1) prepare material:
A) maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, styrene and polymerization inhibitor are weighed in proportion Agent, it is spare；
B) weigh in proportion phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, polyvinyl alcohol, Gelatin, terephthalaldehyde and modifying agent, it is spare；
2) phosphoric acid for taking step 1) to prepare, deionized water dissolving are simultaneously configured to phosphoric acid solution, put into three-necked flask, heating Heating, is added the aluminium hydroxide that step 1) prepares, stirring in batches, and constant-temperature condensation reflux 2-3h obtains first material；
3) first material of step 2) preparation is taken, baking oven is dried at 90-100 DEG C, is ground into powder, then put into Muffle furnace In, it is sintered 3-3.5h, sintering temperature is 400-410 DEG C, obtains second material；
4) 2/3 maleic anhydride for taking step 1) to prepare is put into three-necked flask, and heating is heated to 95-105 DEG C, is stirred Device stirring is mixed, is continuously heating to 180-185 DEG C, the dicyclopentadiene of step 1) preparation is slowly added dropwise, reacts 20-30min, then add Add phthalic anhydride, propylene glycol is added batch-wise, remaining 1/3 maleic anhydride is added after reacting 1-1.2h, the reaction was continued, Every 1-1.5h tests acid value when reaction, and reaction was completed when acid value is down to 30-40mgKOH/g, then is cooled to 170-180 DEG C, Polymerization inhibitor is added, styrene is added when being cooled to 120-130 DEG C, stirs evenly, obtains third material；
5) polyvinyl alcohol, gelatin, mixing is mixed using deionized water in polyvinyl alcohol, the gelatin for taking step 1) to prepare Swelling is stood after uniformly, then is warming up to 80-90 DEG C, constant temperature dissolution adds terephthalaldehyde, after being stirred to react 4-6h, stands, Filtering obtains wet gel, then by wet gel washing and drying, obtains 4 materials；
6) 4 materials prepared by second material, the third material of step 4) preparation, the step 5) for taking step 3) to prepare, are mixed It closes uniformly, stirs 30-50min, sequentially add aluminium oxide, silica, magnesium dioxide and modifying agent, be warming up to 100-110 DEG C, 20-30min is stirred, glass fibre is added, ultrasonic disperse 20-30min is cooling, obtains finished product.
Optimally, comprising the following steps:
1) prepare material:
A) maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, styrene and polymerization inhibitor are weighed in proportion Agent, it is spare；
B) weigh in proportion phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, polyvinyl alcohol, Gelatin, terephthalaldehyde and modifying agent, it is spare；Prepare each component raw material in the technical program step 1), is convenient for operator Carry out subsequent step operation；
2) phosphoric acid for taking step 1) to prepare, deionized water dissolving are simultaneously configured to phosphoric acid solution, put into three-necked flask, heating It is heated to 80-90 DEG C, the aluminium hydroxide that step 1) prepares is added in batches, stirs 30-40min, constant-temperature condensation reflux 2-3h is obtained To first material；Reacted using phosphoric acid and aluminium hydroxide in the technical program step 2), generate aluminum phosphate, at this time A1 content compared with It is more, it has been primarily formed in first material with Al (H2PO4)3With A1 (HPO4)3Mixture, viscosity is larger, can effectively play bonding The effect of each component；
3) first material of step 2) preparation is taken, baking oven is dried at 90-100 DEG C, is ground into powder, then put into Muffle furnace In, it is sintered 3-3.5h, sintering temperature is 400-410 DEG C, obtains second material；In the technical program step 3) by first material into Row sintering, during the sintering process, Al (H2PO4)3Heated condensation reaction generates aluminium triphosphate and its crystalline hydrate, P-O-H with P-O-H sloughs an one's share of expenses for a joint undertaking water, becomes linear P-O-P key；400-410 DEG C is set by sintering temperature in the technical program, Al (H2PO4)3Start the aluminium metaphosphate of generation hexagonal crystal system, linear P-O-P key becomes cricoid linear P-O-P key, at this time the second object Material is the mixture of aluminium metaphosphate, aluminium triphosphate and two water aluminium triphosphates, wherein also adulterating a small amount of aluminium dihydrogen phosphate；
4) 2/3 maleic anhydride for taking step 1) to prepare is put into three-necked flask, and heating is heated to 95-105 DEG C, is stirred Device stirring is mixed, is continuously heating to 180-185 DEG C, the dicyclopentadiene of step 1) preparation is slowly added dropwise, reacts 20-30min, then add Add phthalic anhydride, propylene glycol is added batch-wise, remaining 1/3 maleic anhydride is added after reacting 1-1.2h, the reaction was continued, Every 1-1.5h tests acid value when reaction, and reaction was completed when acid value is down to 30-40mgKOH/g, then is cooled to 170-180 DEG C, Polymerization inhibitor is added, styrene is added when being cooled to 120-130 DEG C, stirs evenly, obtains third material；The technical program step 4) Middle linear polyester, with vinyl monomer crosslinking curing, forms the resin of netted body structure under initiator, promotor effect, Wherein select styrene for crosslinking agent, styrene reactivity is strong, and the intermiscibility of good mechanical property and various kinds of resin is preferable；This skill Resin is modified using dicyclopentadiene in art scheme, the heat resistance and mechanical property of resin can be effectively improved；
5) polyvinyl alcohol, gelatin, stirring is mixed using deionized water in polyvinyl alcohol, the gelatin for taking step 1) to prepare Time is 15-25min, stands swelling after mixing, then be warming up to 80-90 DEG C, and constant temperature dissolves 1-1.2h, is added to benzene two Formaldehyde after being stirred to react 4-6h, stands 4-6h, and filtering obtains wet gel, then by wet gel washing and drying, obtains 4 materials； It is prepared wet solidifying as matrix using terephthalaldehyde as crosslinking agent in the technical program using polyvinyl alcohol and gelatin Glue primarily serves cementation；The presence of gel network simultaneously can be used for guaranteeing the dispersibility of each component raw material, avoid sending out Raw component agglomeration；
6) 4 materials prepared by second material, the third material of step 4) preparation, the step 5) for taking step 3) to prepare, are mixed It closes uniformly, stirs 30-50min in 1500-2500r/min, sequentially add aluminium oxide, silica, magnesium dioxide and modification Agent is warming up to 100-110 DEG C, stirs 20-30min, adds glass fibre, and ultrasonic disperse 20-30min is cooling, obtains into Product.Filler can be added in step 6) in the technical program, and inorganic filler and the addition of glass fibre can effectively improve the toughness of resin And intensity；During adding filler, aluminium oxide, silica, magnesium dioxide surface are swashed using modifying agent and are modified, is made Aluminium oxide, silica, magnesium dioxide can crosslinking preferably compatible with organic material, while the presence of gel network again pole Agglomeration occurs for avoid aluminium oxide, silica, the magnesium dioxide of big degree；The present invention is in whipping process, the second object Remaining aluminium dihydrogen phosphate can generate aluminium metaphosphate with oxidation reactive aluminum in material, and stirring polymerization forms three-dimensional net structure, reduces Remaining impurity in material, further improves the high tenacity of entire resin.
Compared with prior art, the beneficial effects of the present invention are:
The technical program is reacted first with using phosphoric acid and aluminium hydroxide, generates Al (H2PO4)3With Al (HPO4)3It is mixed Object is closed, sintering process is recycled, by the Al (H in mixture2PO4)3It is converted into the aluminium metaphosphate of hexagonal crystal system, aluminium metaphosphate is viscous It is strong to tie performance, stable structure；Followed by polyvinyl alcohol and gelatin as matrix, using terephthalaldehyde as crosslinking agent, system It is standby to obtain wet gel；Followed by linear polyester crosslinking curing, the resin matrix of netted body structure is formed；It will finally be prepared into To aluminium metaphosphate mixture, gel be separately added into resin matrix, due to the stable structure of aluminium metaphosphate, aluminum phosphate, have Preferable high temperature resistance effectively increases the heat-resisting quantity of resin；Aluminium metaphosphate mixture has preferable adhesive property, can Cooperation gel network plays cementation together, guarantees the compatibility between component, while the presence of gel network can rise again To the effect for preventing each component from reuniting, guarantee that each component raw material being capable of homogeneous reaction crosslinking；Inorganic filler aluminium oxide, titanium dioxide The addition of silicon, magnesium dioxide and glass fibre further improves the toughness and intensity of resin, while also improving the resistance to of resin Grind performance；There is also aluminium triphosphate in aluminium metaphosphate mixture in the technical program, aluminium triphosphate can be with metal ion knot Conjunction forms complex compound, has passivation to metal, and in the working environment of Anchor Agent resin there are more metal from Son, the presence of aluminium triphosphate can effectively improve the corrosion resistance of resin.
The present invention devises a kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof, in preparing resin raw material Inorganic filler is added, realizes organic and inorganic doping, the intensity and toughness of resin can be effectively improved；Phosphoric acid, hydroxide are utilized simultaneously Reactive aluminum generates the components such as aluminium triphosphate, aluminium metaphosphate, these components have preferable high temperature resistance, can effectively improve tree The high temperature resistance of rouge, each raw material component is at low cost, economical and practical, has preferable practicability.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
Embodiment 1:
Prepare material first, weighs maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, benzene in proportion Ethylene and polymerization inhibitor, it is spare；Weigh in proportion phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, Polyvinyl alcohol, gelatin, terephthalaldehyde and modifying agent, it is spare；
Phosphoric acid is taken again, deionized water dissolving is simultaneously configured to phosphoric acid solution, puts into three-necked flask, and heating is heated to 80 DEG C, Aluminium hydroxide is added in batches, stirs 30min, constant-temperature condensation reflux 2h obtains first material；First material is taken, is dried at 90 DEG C Case drying, is ground into powder, then put into Muffle furnace, is sintered 3h, and sintering temperature is 400 DEG C, obtains second material；
Then 2/3 maleic anhydride is taken, is put into three-necked flask, heating is heated to 95 DEG C, blender stirring, after of continuing rising Dicyclopentadiene is slowly added dropwise to 180 DEG C in temperature, reacts 20min, then add phthalic anhydride, propylene glycol is added batch-wise, and reacts Remaining 1/3 maleic anhydride is added after 1h, the reaction was continued, and when reaction, every 1h tested acid value, until acid value is down to Reaction was completed when 30mgKOH/g, then is cooled to 170 DEG C, and polymerization inhibitor is added, and styrene is added when being cooled to 120 DEG C, and stirring is equal It is even, obtain third material；
Take polyvinyl alcohol, gelatin again, using deionized water be mixed polyvinyl alcohol, gelatin, mixing time 15min, Swelling is stood after mixing, then is warming up to 80 DEG C, and constant temperature dissolves 1h, adds terephthalaldehyde, after being stirred to react 4h, stands 4h, filtering obtain wet gel, then by wet gel washing and drying, obtain 4 materials；
The second material of preparation, the third material of preparation, the 4 materials prepared are taken again, are uniformly mixed, in 1500r/min 30min is stirred, aluminium oxide, silica, magnesium dioxide and modifying agent are sequentially added, is warming up to 100 DEG C, stirs 20min, then Glass fibre is added, ultrasonic disperse 20min is cooling, obtains finished product.
High tenacity resin each raw material component is as follows in embodiment 1: by weight, 20 parts of maleic anhydride, bicyclic penta 2 5 parts of alkene, 5 parts of phthalic anhydride, 3 parts of propylene glycol, 6 parts of styrene, 1 part of polymerization inhibitor, 5 parts of binder, 12 parts of additive.
Wherein additive each raw material component is as follows: by weight, 80 parts of phosphoric acid, 25 parts of aluminium hydroxide, 5 parts of glass fibre and 10 parts of filler；Filler each raw material component is as follows: by weight, 15 parts of aluminium oxide, 6 parts of silica, 1 part of magnesia, modifying agent 3 Part；Binder each raw material component is as follows: by weight, 10 parts of polyvinyl alcohol, 4 parts of gelatin and 1 part of terephthalaldehyde.
Wherein the polymerization inhibitor is hydroquinone；The modifying agent is Silane coupling reagent KH-570.
Embodiment 2:
Prepare material first, weighs maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, benzene in proportion Ethylene and polymerization inhibitor, it is spare；Weigh in proportion phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, Polyvinyl alcohol, gelatin, terephthalaldehyde and modifying agent, it is spare；
Phosphoric acid is taken again, deionized water dissolving is simultaneously configured to phosphoric acid solution, puts into three-necked flask, and heating is heated to 85 DEG C, Aluminium hydroxide is added in batches, stirs 35min, constant-temperature condensation reflux 2.5h obtains first material；First material is taken, at 94 DEG C Baking oven drying, is ground into powder, then put into Muffle furnace, is sintered 3.3h, and sintering temperature is 405 DEG C, obtains second material；
Then 2/3 maleic anhydride is taken, is put into three-necked flask, heating is heated to 100 DEG C, and blender stirring continues 183 DEG C are warming up to, dicyclopentadiene is slowly added dropwise, 25min is reacted, then add phthalic anhydride, propylene glycol is added batch-wise, instead Remaining 1/3 maleic anhydride is added after answering 1.1h, the reaction was continued, and when reaction, every 1.2h tested acid value, until acid value is down to Reaction was completed when 35mgKOH/g, then is cooled to 175 DEG C, and polymerization inhibitor is added, and styrene is added when being cooled to 125 DEG C, and stirring is equal It is even, obtain third material；
Take polyvinyl alcohol, gelatin again, using deionized water be mixed polyvinyl alcohol, gelatin, mixing time 20min, Swelling is stood after mixing, then is warming up to 85 DEG C, and constant temperature dissolves 1.1h, adds terephthalaldehyde, quiet after being stirred to react 5h 5h is set, is filtered, obtains wet gel, then by wet gel washing and drying, obtain 4 materials；
The second material of preparation, the third material of preparation, the 4 materials prepared are taken again, are uniformly mixed, in 2000r/min 40min is stirred, aluminium oxide, silica, magnesium dioxide and modifying agent are sequentially added, is warming up to 105 DEG C, stirs 25min, then Glass fibre is added, ultrasonic disperse 25min is cooling, obtains finished product.
High tenacity resin each raw material component is as follows in embodiment 1: by weight, 30 parts of maleic anhydride, bicyclic penta 2 10 parts of alkene, 7 parts of phthalic anhydride, 5 parts of propylene glycol, 12 parts of styrene, 2 parts of polymerization inhibitor, 7 parts of binder, 15 parts of additive.
Wherein additive each raw material component is as follows: by weight, 0 part of phosphatase 79,28 parts of aluminium hydroxide, 14 parts of glass fibre With 18 parts of filler；Filler each raw material component is as follows: by weight, 18 parts of aluminium oxide, 3 parts of magnesia, is modified 0 part of silica 1 4 parts of agent；Binder each raw material component is as follows: by weight, 13 parts of polyvinyl alcohol, 6 parts of gelatin and 1.5 parts of terephthalaldehyde.
Wherein the polymerization inhibitor is hydroquinone；The modifying agent is Silane coupling reagent KH-570.
Embodiment 3:
Prepare material first, weighs maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, benzene in proportion Ethylene and polymerization inhibitor, it is spare；Weigh in proportion phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, Polyvinyl alcohol, gelatin, terephthalaldehyde and modifying agent, it is spare；
Phosphoric acid is taken again, deionized water dissolving is simultaneously configured to phosphoric acid solution, puts into three-necked flask, and heating is heated to 90 DEG C, Aluminium hydroxide is added in batches, stirs 40min, constant-temperature condensation reflux 3h obtains first material；First material is taken, is dried at 100 DEG C Case drying, is ground into powder, then put into Muffle furnace, is sintered 3.5h, and sintering temperature is 410 DEG C, obtains second material；
Then 2/3 maleic anhydride is taken, is put into three-necked flask, heating is heated to 105 DEG C, and blender stirring continues 185 DEG C are warming up to, dicyclopentadiene is slowly added dropwise, 30min is reacted, then add phthalic anhydride, propylene glycol is added batch-wise, instead Remaining 1/3 maleic anhydride is added after answering 1.2h, the reaction was continued, and when reaction, every 1.5h tested acid value, until acid value is down to Reaction was completed when 40mgKOH/g, then is cooled to 180 DEG C, and polymerization inhibitor is added, and styrene is added when being cooled to 130 DEG C, and stirring is equal It is even, obtain third material；
Take polyvinyl alcohol, gelatin again, using deionized water be mixed polyvinyl alcohol, gelatin, mixing time 25min, Swelling is stood after mixing, then is warming up to 90 DEG C, and constant temperature dissolves 1.2h, adds terephthalaldehyde, quiet after being stirred to react 6h 6h is set, is filtered, obtains wet gel, then by wet gel washing and drying, obtain 4 materials；
The second material of preparation, the third material of preparation, the 4 materials prepared are taken again, are uniformly mixed, in 2500r/min 50min is stirred, aluminium oxide, silica, magnesium dioxide and modifying agent are sequentially added, is warming up to 110 DEG C, stirs 30min, then Glass fibre is added, ultrasonic disperse 30min is cooling, obtains finished product.
High tenacity resin each raw material component is as follows in embodiment 1: by weight, 40 parts of maleic anhydride, bicyclic penta 2 15 parts of alkene, 10 parts of phthalic anhydride, 6 parts of propylene glycol, 14 parts of styrene, 3 parts of polymerization inhibitor, 10 parts of binder, 18 parts of additive.
Wherein additive each raw material component is as follows: by weight, 00 part of phosphatase 11,30 parts of aluminium hydroxide, 18 parts of glass fibre With 25 parts of filler；Filler each raw material component is as follows: by weight, 20 parts of aluminium oxide, 5 parts of magnesia, is modified 4 parts of silica 1 5 parts of agent；Binder each raw material component is as follows: by weight, 15 parts of polyvinyl alcohol, 8 parts of gelatin and 2 parts of terephthalaldehyde
Wherein the polymerization inhibitor is hydroquinone；The modifying agent is Silane coupling reagent KH-570.
Embodiment 4:
Prepare material first, weighs maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, benzene in proportion Ethylene and polymerization inhibitor, it is spare；Phosphoric acid, aluminium hydroxide, polyvinyl alcohol, gelatin, terephthalaldehyde are weighed in proportion, it is spare；
Phosphoric acid is taken again, deionized water dissolving is simultaneously configured to phosphoric acid solution, puts into three-necked flask, and heating is heated to 85 DEG C, Aluminium hydroxide is added in batches, stirs 35min, constant-temperature condensation reflux 2.5h obtains first material；First material is taken, at 94 DEG C Baking oven drying, is ground into powder, then put into Muffle furnace, is sintered 3.3h, and sintering temperature is 405 DEG C, obtains second material；
Then 2/3 maleic anhydride is taken, is put into three-necked flask, heating is heated to 100 DEG C, and blender stirring continues 183 DEG C are warming up to, dicyclopentadiene is slowly added dropwise, 25min is reacted, then add phthalic anhydride, propylene glycol is added batch-wise, instead Remaining 1/3 maleic anhydride is added after answering 1.1h, the reaction was continued, and when reaction, every 1.2h tested acid value, until acid value is down to Reaction was completed when 35mgKOH/g, then is cooled to 175 DEG C, and polymerization inhibitor is added, and styrene is added when being cooled to 125 DEG C, and stirring is equal It is even, obtain third material；
Take polyvinyl alcohol, gelatin again, using deionized water be mixed polyvinyl alcohol, gelatin, mixing time 20min, Swelling is stood after mixing, then is warming up to 85 DEG C, and constant temperature dissolves 1.1h, adds terephthalaldehyde, quiet after being stirred to react 5h 5h is set, is filtered, obtains wet gel, then by wet gel washing and drying, obtain 4 materials；
The second material of preparation, the third material of preparation, the 4 materials prepared are taken again, are uniformly mixed, in 2000r/min 40min is stirred, finished product is obtained.
High tenacity resin each raw material component is as follows in embodiment 1: by weight, 30 parts of maleic anhydride, bicyclic penta 2 10 parts of alkene, 7 parts of phthalic anhydride, 5 parts of propylene glycol, 12 parts of styrene, 2 parts of polymerization inhibitor, 7 parts of binder, 15 parts of additive.
Wherein additive each raw material component is as follows: by weight, 0 part of phosphatase 79,28 parts of aluminium hydroxide；Each raw material of binder Component is as follows: by weight, 13 parts of polyvinyl alcohol, 6 parts of gelatin and 1.5 parts of terephthalaldehyde.Wherein the polymerization inhibitor is to benzene Diphenol.
Embodiment 5:
Prepare material first, weighs maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, benzene in proportion Ethylene and polymerization inhibitor, it is spare；Polyvinyl alcohol, gelatin, terephthalaldehyde are weighed in proportion, it is spare；
2/3 maleic anhydride is taken first, is put into three-necked flask, and heating is heated to 100 DEG C, and blender stirring continues 183 DEG C are warming up to, dicyclopentadiene is slowly added dropwise, 25min is reacted, then add phthalic anhydride, propylene glycol is added batch-wise, instead Remaining 1/3 maleic anhydride is added after answering 1.1h, the reaction was continued, and when reaction, every 1.2h tested acid value, until acid value is down to Reaction was completed when 35mgKOH/g, then is cooled to 175 DEG C, and polymerization inhibitor is added, and styrene is added when being cooled to 125 DEG C, and stirring is equal It is even, obtain third material；
Take polyvinyl alcohol, gelatin again, using deionized water be mixed polyvinyl alcohol, gelatin, mixing time 20min, Swelling is stood after mixing, then is warming up to 85 DEG C, and constant temperature dissolves 1.1h, adds terephthalaldehyde, quiet after being stirred to react 5h 5h is set, is filtered, obtains wet gel, then by wet gel washing and drying, obtain 4 materials；
The third material of preparation, the 4 materials of preparation are taken again, is uniformly mixed, and are stirred 40min in 2000r/min, are obtained Finished product.
High tenacity resin each raw material component is as follows in embodiment 1: by weight, 30 parts of maleic anhydride, bicyclic penta 2 10 parts of alkene, 7 parts of phthalic anhydride, 5 parts of propylene glycol, 12 parts of styrene, 2 parts of polymerization inhibitor, 7 parts of binder.
Wherein binder each raw material component is as follows: by weight, 13 parts of polyvinyl alcohol, 6 parts of gelatin and terephthalaldehyde 1.5 Part.Wherein the polymerization inhibitor is hydroquinone.
Experiment:
The resin sample of Example 1-5 preparation, then the unsaturated polyester resin sample bought from market is taken, it is right respectively It, which carries out heat-resisting quantity, compression strength, corrosion resistance, can be carried out detection, and detection data is as follows:
Conclusion: embodiment 1-3 is technical solution of the present invention, in embodiment 4 and is not added with inorganic filler and glass fibre, real Inorganic filler and glass fibre are applied in example 5 and be not added with, while and the raw materials such as phosphoric acid are not used；
The data of sample are bought it is found that the heat-resisting quantity in embodiment 1-3 is substantially better than in comparative example 1-5 and market Embodiment 4, embodiment 5, and the high temperature resistance of embodiment 4-5, better than the sample in market, this has absolutely proved that reaction generates Aluminium metaphosphate, aluminum phosphate stable structure, have preferable high temperature resistance, effectively increase the heat-resisting quantity of resin.
Compression strength in embodiment 1-3 is substantially better than embodiment 4, embodiment 5, and the compression strength of embodiment 4 is obvious Better than the compression strength in embodiment 5, the compression strength in embodiment 5 is better than the sample in market, this has absolutely proved inorganic The addition of filling alumina, silica, magnesium dioxide and glass fibre further improves the toughness and intensity of resin.
The present invention devises a kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof, in preparing resin raw material Inorganic filler is added, realizes organic and inorganic doping, the intensity and toughness of resin can be effectively improved；Phosphoric acid, hydroxide are utilized simultaneously Reactive aluminum generates the components such as aluminium triphosphate, aluminium metaphosphate, these components have preferable high temperature resistance, can effectively improve tree The high temperature resistance of rouge, each raw material component is at low cost, economical and practical, has preferable practicability.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims Variation is included within the present invention.Any label in claim should not be construed as limiting the claims involved.

Claims (8)

1. a kind of Anchor Agent high temperature resistant high tenacity resin, it is characterised in that: the high tenacity resin each raw material component is as follows: with Poidometer, 20-40 parts of maleic anhydride, 5-15 parts of dicyclopentadiene, 5-10 parts of phthalic anhydride, 3-6 parts of propylene glycol, benzene 6-14 parts of ethylene, 1-3 parts of polymerization inhibitor, 5-10 parts of binder, 12-18 parts of additive.
2. a kind of Anchor Agent according to claim 1 high temperature resistant high tenacity resin, it is characterised in that: the additive is each Raw material components are as follows: by weight, 80-100 parts of phosphoric acid, 25-30 parts of aluminium hydroxide, 5-18 parts of glass fibre and filler 10-25 Part.
3. a kind of Anchor Agent according to claim 2 high temperature resistant high tenacity resin, it is characterised in that: each original of filler Expect that component is as follows: by weight, 15-20 parts of aluminium oxide, 6-14 parts of silica, 1-5 parts of magnesia, 3-5 parts of modifying agent.
4. a kind of Anchor Agent according to claim 3 high temperature resistant high tenacity resin, it is characterised in that: the binder is each Raw material components are as follows: by weight, 10-15 parts of polyvinyl alcohol, 4-8 parts of gelatin and 1-2 parts of terephthalaldehyde.
5. a kind of Anchor Agent according to claim 4 high temperature resistant high tenacity resin, it is characterised in that: the polymerization inhibitor is Hydroquinone；The modifying agent is Silane coupling reagent KH-570.
6. a kind of Anchor Agent preparation method of high temperature resistant high tenacity resin, it is characterised in that: the following steps are included:
1) prepare material:
2) phosphoric acid for taking step 1) to prepare, is configured to phosphoric acid solution, and the hydroxide that step 1) prepares is added in heating heating in batches Aluminium, stirring, constant-temperature condensation reflux obtain first material；
3) first material for taking step 2) to prepare, drying grinding, is sintered 3-3.5h, obtains second material；
4) 2/3 maleic anhydride for taking step 1) to prepare, heating heating, blender stirring are continuously heating to, step are slowly added dropwise The rapid dicyclopentadiene 1) prepared, reaction, then phthalic anhydride is added, propylene glycol is added batch-wise, is added after reaction remaining 1/3 maleic anhydride reaction a period of time, is cooled to 170-180 DEG C, polymerization inhibitor is added, is cooled to 120- after reaction was completed Styrene is added at 130 DEG C, stirs evenly, obtains third material；
5) polyvinyl alcohol, the gelatin for taking step 1) to prepare are mixed polyvinyl alcohol, gelatin using deionized water, stand swelling, Rising temperature for dissolving is added terephthalaldehyde, is stirred to react, and stands, and filters, and washs, dry, obtains 4 materials；
6) 4 materials prepared by second material, the third material of step 4) preparation, the step 5) for taking step 3) to prepare, mixing are equal It is even, aluminium oxide, silica, magnesium dioxide and modifying agent are sequentially added, heating stirring adds glass fibre, ultrasound point It dissipates, it is cooling, obtain finished product.
7. a kind of preparation method of Anchor Agent high temperature resistant high tenacity resin according to claim 6, it is characterised in that: packet Include following steps:
1) prepare material:
A) maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, styrene and polymerization inhibitor are weighed in proportion, it is standby With；
B) phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, polyvinyl alcohol, bright is weighed in proportion Glue, terephthalaldehyde and modifying agent, it is spare；
2) phosphoric acid for taking step 1) to prepare, deionized water dissolving are simultaneously configured to phosphoric acid solution, put into three-necked flask, and heating adds Heat, is added the aluminium hydroxide that step 1) prepares, stirring in batches, and constant-temperature condensation reflux 2-3h obtains first material；
3) first material of step 2) preparation is taken, baking oven is dried at 90-100 DEG C, it is ground into powder, then put into Muffle furnace, It is sintered 3-3.5h, sintering temperature is 400-410 DEG C, obtains second material；
4) 2/3 maleic anhydride for taking step 1) to prepare is put into three-necked flask, and heating is heated to 95-105 DEG C, blender Stirring, is continuously heating to 180-185 DEG C, and the dicyclopentadiene of step 1) preparation is slowly added dropwise, and reacts 20-30min, then add neighbour Propylene glycol is added batch-wise in phthalate anhydride, and remaining 1/3 maleic anhydride is added after reacting 1-1.2h, and the reaction was continued, reaction When every 1-1.5h test acid value, reaction was completed when until acid value being down to 30-40mgKOH/g, then is cooled to 170-180 DEG C, is added Polymerization inhibitor is added styrene when being cooled to 120-130 DEG C, stirs evenly, and obtains third material；
5) polyvinyl alcohol, the gelatin for taking step 1) to prepare are mixed polyvinyl alcohol, gelatin using deionized water, are uniformly mixed Swelling is stood afterwards, then is warming up to 80-90 DEG C, and constant temperature dissolution adds terephthalaldehyde, after being stirred to react 4-6h, stands, mistake Filter obtains wet gel, then by wet gel washing and drying, obtains 4 materials；
6) 4 materials prepared by second material, the third material of step 4) preparation, the step 5) for taking step 3) to prepare, mixing are equal It is even, 30-50min is stirred, aluminium oxide, silica, magnesium dioxide and modifying agent is sequentially added, is warming up to 100-110 DEG C, stir 20-30min is mixed, glass fibre is added, ultrasonic disperse 20-30min is cooling, obtains finished product.
8. a kind of preparation method of Anchor Agent high temperature resistant high tenacity resin according to claim 7, it is characterised in that: packet Include following steps:
1) prepare material:
A) maleic anhydride, dicyclopentadiene, phthalic anhydride, propylene glycol, styrene and polymerization inhibitor are weighed in proportion, it is standby With；
B) phosphoric acid, aluminium hydroxide, aluminium oxide, silica, magnesium dioxide, glass fibre, polyvinyl alcohol, bright is weighed in proportion Glue, terephthalaldehyde and modifying agent, it is spare；
2) phosphoric acid for taking step 1) to prepare, deionized water dissolving are simultaneously configured to phosphoric acid solution, put into three-necked flask, heating heating To 80-90 DEG C, the aluminium hydroxide that step 1) prepares is added in batches, stirs 30-40min, constant-temperature condensation flows back 2-3h, obtains the One material；
3) first material of step 2) preparation is taken, baking oven is dried at 90-100 DEG C, it is ground into powder, then put into Muffle furnace, It is sintered 3-3.5h, sintering temperature is 400-410 DEG C, obtains second material；
4) 2/3 maleic anhydride for taking step 1) to prepare is put into three-necked flask, and heating is heated to 95-105 DEG C, blender Stirring, is continuously heating to 180-185 DEG C, and the dicyclopentadiene of step 1) preparation is slowly added dropwise, and reacts 20-30min, then add neighbour Propylene glycol is added batch-wise in phthalate anhydride, and remaining 1/3 maleic anhydride is added after reacting 1-1.2h, and the reaction was continued, reaction When every 1-1.5h test acid value, reaction was completed when until acid value being down to 30-40mgKOH/g, then is cooled to 170-180 DEG C, is added Polymerization inhibitor is added styrene when being cooled to 120-130 DEG C, stirs evenly, and obtains third material；
5) polyvinyl alcohol, gelatin, mixing time is mixed using deionized water in polyvinyl alcohol, the gelatin for taking step 1) to prepare For 15-25min, swelling is stood after mixing, then is warming up to 80-90 DEG C, and constant temperature dissolves 1-1.2h, adds terephthaldehyde Aldehyde after being stirred to react 4-6h, stands 4-6h, and filtering obtains wet gel, then by wet gel washing and drying, obtains 4 materials；
6) 4 materials prepared by second material, the third material of step 4) preparation, the step 5) for taking step 3) to prepare, mixing are equal It is even, 30-50min is stirred in 1500-2500r/min, sequentially adds aluminium oxide, silica, magnesium dioxide and modifying agent, is risen Temperature stirs 20-30min to 100-110 DEG C, adds glass fibre, and ultrasonic disperse 20-30min is cooling, obtains finished product.
CN201910465937.9A 2019-05-30 2019-05-30 A kind of Anchor Agent high temperature resistant high tenacity resin and preparation method thereof Pending CN110128987A (en)

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Application publication date: 20190816