CN109053997A - A kind of aliphatic hyperbranched epoxy resin and preparation method thereof - Google Patents
A kind of aliphatic hyperbranched epoxy resin and preparation method thereof Download PDFInfo
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- CN109053997A CN109053997A CN201810627552.3A CN201810627552A CN109053997A CN 109053997 A CN109053997 A CN 109053997A CN 201810627552 A CN201810627552 A CN 201810627552A CN 109053997 A CN109053997 A CN 109053997A
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- epoxy resin
- hyperbranched epoxy
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/04—Polyamides derived from alpha-amino carboxylic acids
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of aliphatic hyperbranched epoxy resins and preparation method thereof.A kind of aliphatic hyperbranched epoxy resin of the present invention uses polyol compound and epoxide for monomer, pass through bulk polymerization, Proton-Transfer Reactions, one-step method obtains a kind of aliphatic hyperbranched epoxy resin, a kind of epoxide number of aliphatic hyperbranched epoxy resin provided by the invention is 0.2 ~ 0.3 mol/100g, weight average molecular weight is 3000 ~ 6000 g/mol, and the degree of branching is 0.3 ~ 0.6.A kind of kernel of aliphatic hyperbranched epoxy resin contains great amount of hydroxy group, and epoxy-functional is contained in outer end, and aliphatic hyperbranched epoxy resin of the invention can be used as modifying agent and further promote high molecular material performance.Present invention process is simple, and product purity is high, and yield is high, does not need complicated purification operations.
Description
Technical field
The present invention relates to resins synthesis technical field, more particularly, to a kind of aliphatic hyperbranched epoxy resin and its
Preparation method.
Background technique
High-performance thermosetting resin is current most popular advanced composite material matrix, composite material with lightweight,
Height is than strong, Gao Bimo, high-temperature resistant and extremely strong material property designability, and as one of developing High-tech Material,
Application in Aeronautics and Astronautics industry also shows unique advantage and potentiality, is the weight of Aeronautics and Astronautics material technology progress
Indicate.With the increase of thermosetting resin based composites usage amount, drawback also gradually appears, and maximum problem is brittleness
Greatly, impact resistant strength is low, is easy cracking.It is high-new in Aeronautics and Astronautics etc. that these disadvantages significantly limit high performance structures material
The promotion and application of technical field.Therefore, it is necessary to be modified to thermosetting resin, on the basis of its original excellent properties
On, the high-performance thermosetting resin system of new generation of exploitation low viscosity, Qiang Erren.
Dissaving polymer has highly branched structure, and molecule is in elliposoidal, and molecule chain end has a large amount of function
Group, thus shows the performance different from line polymer, such as the viscosity of strand not easy entanglement, solution and ontology is low etc..
The unique property of dissaving polymer and relatively simple synthetic method make it show tempting application prospect.Hyperbranched polymerization
Object can be used as New Processing Aid, rheology modifier and toughener of thermosetting resin etc., the conjunction of novel hyperbranched polymer
At and its to improve the research of resin property be one of hot spot in recent years.
For the Boltorn series hyperbranched epoxy resin that Perstorp company of Switzerland develops, the hyperbranched epoxy of the series
Resin controls molecular weight and distribution using ethoxylated pentaerythritol as kernel, using dihydromethyl propionic acid as AB2Type monomer into
Hydroxyl hyper-branched polyester is made from polycondensation in row, and then hydroxyl telechelic polyester carries out epoxy with epichlorohydrin reaction under highly basic
Sealing end obtains polyester type hyperbranched epoxy resin.The hyperbranched epoxy resin synthetic route prepared by two-step method is longer, technique
It is more complex and at high cost.In addition alternative AB2Type monomeric species are limited, it more difficult in progress structure design.
Summary of the invention
The technical solution adopted by the present invention is that: a kind of aliphatic hyperbranched epoxy resin, by polyol compound and epoxy
The monomer bulk polymerization of compound forms:
The polyol compound is shown in having structure Formulas I:
I:
Wherein, R1~R4In, at least three substituent groups areResidue replaces
Base is C1~C6Alkyl；Wherein, Z isThe n0~n3For 1~3 integer；
The epoxide is shown in having structure Formula II:
II:
Wherein, R5~R8In, at least three substituent groups are Remaining substituent group is H or C1~C6Alkyl；The n4~n7For 1~3 integer.
The aliphatic hyperbranched epoxy resin specifically includes following preparation step:
S1. polyol compound and epoxide are added in reactor, and catalyst is added thereto, be filled with guarantor
It protects under gas, slowly heats up, it is cooling after reaction；
S2. solvent is added into step S1 products therefrom, dissolves, stirs and pour into deionized water, stratification；
S3. it takes the lower liquid being layered in step S2 that desiccant is added, dries, filters, distill hyperbranched to get aliphatic
Epoxy resin.
Aliphatic hyperbranched resin of the invention utilizes polyol compound and epoxide bulk polymerization, is turned by proton
Reaction is moved, Hyperbranched Epoxy Resin by One-pot Process is prepared by adjusting the proportion of polyol compound and epoxide
Hyperbranched resin contains a large amount of epoxy terminated groups, and active epoxy group can be with amino, carboxylic acid group, phenolic group, alcohol radical, chlorosulfonic acid
A variety of functional group reactions such as base, isocyanate group form crosslinking points, and the quantity influence hyperbranched epoxy resin of epoxy group, which is used as, to be added
Add the performance of agent.
Further, the epoxide number of the aliphatic hyperbranched epoxy resin is 0.2~0.3mol/100g, is divided equally again
Son amount is 3000~6000g/mol, and the degree of branching is 0.3~0.6.
Further, the ratio of the amount of the substance of polyol compound and epoxide described in step S1 is 1:1~4.
Preferably, the ratio of the amount of the substance of polyol compound and epoxide is 1:3.
Further, catalyst described in step S1 is tetrabutylammonium chloride, tetrabutylammonium bromide, methyl tributyl chlorination
Ammonium, etamon chloride, one of 4-propyl ammonium chloride or a variety of promote hydroxyl and epoxy group on lower temperature (100 DEG C of left sides
It is right) under fast reaction.
Further, the additional amount of catalyst described in step S1 is the 1%~10% of the amount of epoxide substance.
Preferably, the additional amount of catalyst is the 5% of the amount of epoxide substance.
Further, reaction temperature described in step S1 is 100~150 DEG C, and the reaction time is 8~for 24 hours, in the temperature and
Reaction time, the bulk polymerization of hyperbranched epoxy resin mildly carry out, and will not generate implode and reaction is incomplete.
Preferably, reaction temperature described in step S1 is 120 DEG C, reaction time 12h.
Further, solvent described in step S2 is tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethylacetamide
One of amine, dimethyl sulfoxide, dioxane are a variety of.
Further, desiccant described in step S3 is one of natrium carbonicum calcinatum, anhydrous sodium sulfate, anhydrous magnesium sulfate
Or it is a variety of.
Further, drying time described in step S3 be 8~for 24 hours.
Preferably, drying time 12h.
Compared with prior art the invention has the following advantages:
A kind of aliphatic hyperbranched epoxy resin provided by the invention uses bulk polymerization, by reaction temperature, reaction
The control of time is reacted it mildly smoothly sufficiently, is prevented because the excessively high formation implode of temperature or reaction time are too short
Lead to reaction not exclusively, simple according to the step production operation, product yield is high, and resulting hyperbranched resin impurity is few,
Product is pure, does not need complicated purification operations.
Aliphatic hyperbranched epoxy resin of the present invention has highly branched structure, is similar to dendritic,
Strand not easy entanglement has compared with low melt viscosity, and high relative to linear polymer surface functional group density.Prepared
Hyperbranched epoxy resin molecular structure is not only without the aromatic structure of phenyl ring, also without alicyclic structure, only saturated aliphatic chain and ehter bond
Structure, the aliphatic chain of saturation make product rich in flexibility and chemical stability, can play the toughness for improving fragile material system,
The ehter bond contained can enhance the stability of system.Aliphatic hyperbranched epoxy resin of the invention can be used for higher processing temperature
Thermal decomposition without causing hyperbranched epoxy resin, in addition, aliphatic hyperbranched epoxy resin of the invention is made in high shear
There is high fluidity with lower, can be used as flow ability modifying agent improves the problem of material flowability difference.
The aliphatic hyperbranched epoxy resin by adjusting polyol compound and epoxide proportion, in strand
Containing a large amount of secondary hydroxyls of regular distribution and the epoxy group of end, therefore interface can be formed with various kinds of resin basis material and handed over
Networking network, solves the problems, such as that modifying agent is incompatible with basis material.The branch of aliphatic hyperbranched epoxy resin is through tree
Among aliphatic radical body, the hydroxyl of kernel can be epoxy terminated by the weak interactions such as hydrogen bond and chemical reaction and matrix collective effect
Can in basis material Cl atom, the groups such as amino, alcohol radical, phenolic group, carboxyl react, increase substantially base as crosslinking agent
Intensity, toughness, heat resistance and the dimensional stability of body material, meanwhile, aliphatic hyperbranched epoxy resin is alternatively arranged as being modified
Agent and flow improver additive improve the processing performance and mechanical strength of the resin matrixes such as benzoxazine, bismaleimide, can reduce
The dosage of other additives.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Pure nylon 6 is purchased from embodiment and comparative example
BASF Co., Ltd, trade mark B3109.All raw materials used in embodiment are commercially available unless otherwise specified.
Embodiment 1
Polyol compound structural formula used is
Epoxy composite structures formula used is
S1: by 12g (0.1mol) trihydroxy methyl ethane and 90.6g (0.3mol) trihydroxymethylpropanyltri diglycidyl ether
It is added in reactor, and 4.17g (0.015mol) tetrabutylammonium chloride is added thereto.Under helium atmosphere protection, slowly
It is cooling after being warming up to 120 DEG C, reaction 12 hours.
S2: 200mL tetrahydrofuran lysate is added, it is poured into deionization while stirring after product is completely dissolved
In water, 3 small layereds are settled.
S3: taking lower liquid that 10g anhydrous sodium sulfate is added, 12 hours dry, and solution is evaporated under reduced pressure, i.e., by filtering
Obtain a kind of aliphatic hyperbranched epoxy resin.
Embodiment 2
Polyol compound structural formula used is
Epoxy composite structures formula used is
S1: 12g (0.1mol) trihydroxy methyl ethane and 108g (0.3mol) pentaerythrite glycidol ether are added to
In reactor, and 8.34g (0.03mol) tetrabutylammonium chloride is added thereto.Under helium atmosphere protection, it is to slowly warm up to
It is cooling after 120 DEG C, reaction 12 hours.
S2: 200mL tetrahydrofuran lysate is added, it is poured into deionization while stirring after product is completely dissolved
In water, 3 small layereds are settled.
S3: taking lower liquid that 10g anhydrous sodium sulfate is added, 12 hours dry, and solution is evaporated under reduced pressure, i.e., by filtering
Obtain a kind of aliphatic hyperbranched epoxy resin.
Embodiment 3
Polyol compound structural formula used is
Epoxy composite structures formula used is
S1: 13.4g (0.1mol) trihydroxy methyl propane and 36g (0.1mol) pentaerythrite glycidol ether are added to
In reactor, and 0.278g (0.001mol) tetrabutylammonium chloride is added thereto.Under helium atmosphere protection, it is to slowly warm up to
It is cooling after 150 DEG C, reaction 8 hours.
S2: 100mL tetrahydrofuran lysate is added, it is poured into deionization while stirring after product is completely dissolved
In water, 3 small layereds are settled.
S3: taking lower liquid to be added 5g anhydrous sodium sulfate, dry 12 hours, filtering, by solution be evaporated under reduced pressure to get
A kind of aliphatic hyperbranched epoxy resin.
Embodiment 4
Polyol compound structural formula used is
Epoxy composite structures formula used is
S1: 13.4g (0.1mol) trihydroxy methyl propane and 120.8g (0.4mol) trimethylolpropane tris are shunk sweet
Oily ether is added in reactor, and 5.56g (0.02mol) tetrabutylammonium chloride is added thereto.Under helium atmosphere protection, delay
Slowly cooling after being warming up to 100 DEG C, reaction 24 hours.
S2: 200mL tetrahydrofuran lysate is added, it is poured into deionization while stirring after product is completely dissolved
In water, 3 small layereds are settled.
S3: taking lower liquid that 10g anhydrous sodium sulfate is added, 12 hours dry, and solution is evaporated under reduced pressure, i.e., by filtering
Obtain a kind of aliphatic hyperbranched epoxy resin.
Embodiment 5
S1., the nylon of 1kg 6 is dried to 5h in 100 DEG C of convection ovens, dry sealing space is subsequently placed to and is cooled to room
Temperature.By the dry 6h of the resulting hyperbranched epoxy resin room temperature in vacuo of embodiment 1, it is then placed into dry sealing space and saves.
S2. dry nylon, 5g hyperbranched epoxy resin are placed in high-speed mixer and are mixed 30 minutes.
S3. 10 temperature control areas of double screw extruder are heated to 220 DEG C of 1st area, 2 225 DEG C of areas, 3 235 DEG C of areas, 4th area~8th area
240 DEG C, 9 230 DEG C of areas, 10 230 DEG C of areas preheat 0.5h.
S4. double screw extruder is added in the mixed material in S2, obtains modification of nylon 6.
Embodiment 6
S1., the nylon of 1kg 6 is dried to 5h in 100 DEG C of convection ovens, dry sealing space is subsequently placed to and is cooled to room
Temperature.By the dry 6h of the resulting hyperbranched epoxy resin room temperature in vacuo of embodiment 3, it is then placed into dry sealing space and saves.
S2. dry nylon, 10g hyperbranched epoxy resin are placed in high-speed mixer and are mixed 30 minutes.
S3. 10 temperature control areas of double screw extruder are heated to 220 DEG C of 1st area, 2 225 DEG C of areas, 3 235 DEG C of areas, 4th area~8th area
240 DEG C, 9 230 DEG C of areas, 10 230 DEG C of areas preheat 0.5h.
S4. double screw extruder is added in the mixed material in S2, obtains modification of nylon 6.
Hyperbranched epoxy resin prepared by embodiment 5, embodiment 6 modified nylon 6 composite material and pure nylon 6 material
Batten injection molding is carried out, it is tested for the property, obtained each performance test standard of 6 test bars of modification of nylon made above is such as
Under: tensile strength is referring to GB/T 1040-2006；Elongation at break is referring to GB/T 1040-2006；Bending strength is referring to GB/T
1040-2008；Bending modulus is referring to GB/T 1040-2008；Cantilever beam impact strength is referring to GB/T 1843-2008；Melting refers to
Number is referring to GB/T3682-2000.Test result is shown in Table 1.
The modified nylon 6 composite material of 1 hyperbranched epoxy resin of table and pure nylon 6 material performance detection
As shown in Table 1, it is compared using the modified nylon 6 composite material intensity of hyperbranched epoxy resin that the present invention synthesizes
Pure nylon 6 is improved into 15%, and melt index improves nearly 30%, it is compound after 6 mechanical property of nylon promoted it is significant.
The technical concept and feature of above-described embodiment only to illustrate the invention, its object is to allow people that can understand the present invention
Content and implement accordingly, it is not intended to limit the scope of the present invention.What all Spirit Essences according to the present invention were done etc.
Effect transformation or modification, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of aliphatic hyperbranched epoxy resin, which is characterized in that the aliphatic hyperbranched epoxy resin is by polynary alcoholization
The monomer for closing object and epoxide is formed through bulk polymerization；
The polyol compound is shown in structural formula I:
I:
Wherein, R1~R4In, at least three substituent groups areRemaining substituent group is
C1~C6Alkyl；Wherein, Z isThe n0~n3For 1~3 integer；
The epoxide is shown in formula II:
II:
Wherein, R5~R8In, at least three substituent groups are Remaining substituent group is H or C1~C6Alkyl；The n4~n7For 1~3 integer.
2. aliphatic hyperbranched epoxy resin according to claim 1 specifically includes following preparation step:
S1. polyol compound and epoxide are added in reactor, and catalyst is added thereto, be filled with protection gas
Body, heating are cooling after reaction；
S2. solvent is added into step S1 products therefrom, dissolves, stirs and pour into deionized water, stratification；
S3. it takes the lower liquid being layered in step S2 that desiccant is added, dries, filters, distill and overspend to get the aliphatic
Change epoxy resin.
3. the aliphatic hyperbranched epoxy resin of preparation according to claim 1 or claim 2, which is characterized in that the aliphatic is super
The epoxide number of branch epoxy resins is 0.2~0.3mol/100g, and weight average molecular weight is 3000~6000g/mol, and the degree of branching is
0.3~0.6.
4. the preparation method according to claim 2 for preparing aliphatic hyperbranched epoxy resin, which is characterized in that step S1
The ratio of the amount of the substance of the polyol compound and epoxide is 1:1~4.
5. the preparation method according to claim 2 for preparing aliphatic hyperbranched epoxy resin, which is characterized in that step S1
The catalyst is tetrabutylammonium chloride, tetrabutylammonium bromide, methyltributylammonichloride chloride, etamon chloride, tetrapropyl
One of ammonium chloride is a variety of.
6. the preparation method according to claim 2 for preparing aliphatic hyperbranched epoxy resin, which is characterized in that step S1
The additional amount of the catalyst is the 1%~10% of the amount of epoxide substance.
7. the preparation method according to claim 2 for preparing aliphatic hyperbranched epoxy resin, which is characterized in that step S1
The reaction temperature be 100~150 DEG C, the reaction time be 8~for 24 hours.
8. the preparation method according to claim 2 for preparing a kind of aliphatic hyperbranched epoxy resin, which is characterized in that step
Solvent described in rapid S2 is tetrahydrofuran, chloroform, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, two
One of six ring of oxygen is a variety of.
9. the preparation method according to claim 2 for preparing aliphatic hyperbranched epoxy resin, which is characterized in that step S3
The desiccant is one of natrium carbonicum calcinatum, anhydrous sodium sulfate, anhydrous magnesium sulfate or a variety of.
10. the preparation method according to claim 2 for preparing aliphatic hyperbranched epoxy resin, which is characterized in that step
Drying time described in S3 be 8~for 24 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109836588A (en) * | 2019-02-27 | 2019-06-04 | 济南大学 | A kind of synthesis of hyperbranched epoxy resin and its application in waterproof roll |
| WO2021004024A1 (en) * | 2019-07-10 | 2021-01-14 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method therefor |
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| CN109836588A (en) * | 2019-02-27 | 2019-06-04 | 济南大学 | A kind of synthesis of hyperbranched epoxy resin and its application in waterproof roll |
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Application publication date: 20181221 |