CN105482078B - Rosin epoxy resin curing agent, its preparation method and application - Google Patents
Rosin epoxy resin curing agent, its preparation method and application Download PDFInfo
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- CN105482078B CN105482078B CN201510845395.XA CN201510845395A CN105482078B CN 105482078 B CN105482078 B CN 105482078B CN 201510845395 A CN201510845395 A CN 201510845395A CN 105482078 B CN105482078 B CN 105482078B
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- 0 CC(C1)C(COCCCS*N)=CC(C)(CC2)C1C(C)(CCC1)C2C1(C)C(O)OCCCS*N Chemical compound CC(C1)C(COCCCS*N)=CC(C)(CC2)C1C(C)(CCC1)C2C1(C)C(O)OCCCS*N 0.000 description 1
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
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Abstract
The invention discloses a kind of rosin epoxy resin curing agent, it is selected from the compound with structure shown in formula I:Wherein, R is aliphatic segment.The invention also discloses the preparation method of the rosin epoxy resin curing agent, its is easy to implement, environmental protection, with low cost.The invention also discloses the purposes of the rosin epoxy resin curing agent, for example by the rosin epoxy resin curing agent and the mixing cured formation solidfied material of epoxy resin, the solidfied material has excellent mechanics and thermal property, recovery of shape speed is fast simultaneously, fixed rate and response rate are high, repeatedly after memory cycle, shape memory effect is good, can the extensive use as shape-memory material.
Description
Technical field
Present invention relates particularly to a kind of rosin epoxy resin curing agent, its preparation method and application, for example, remember in shape
Recall the application of aspect, belong to biological based epoxy curing agent field.
Background technology
The existing thermoset shape memory polymer of polymer with shape memory function, also has thermoplasticity shape memory to gather
Compound.Their difference is that the fixing phase of thermoplasticity shape-memory polymer is physical crosslinking structure, and thermosetting shape
The fixing phase of shape memory polymer is then chemical crosslinking structure.Thermoplasticity shape-memory polymer is circulated by multiple recoverable force
After can decline shape recovery ratio, and its thermomechanical property be difficult meet worked under environment harsh conditions will
Ask.And the shape-memory polymer that epoxy resin is formed with curing agent is because having, and restoring force is big, shape fixed rate is big, response temperature
Easily adjust, the characteristic such as excellent shape-memory properties and disclosure satisfy that work under environment harsh conditions and be widely studied, and
It is with a wide range of applications, the application in the deployable structure of space particularly in Aero-Space.
At present, domestic and international related researcher focuses primarily upon the research of bisphenol A-type shape memory epoxy resin.With right
The continuous research of epoxy resin shape-memory material, finds due to the architectural feature of bisphenol-A epoxy, during as shape-memory material
Flexible component need to be additionally introduced, but it is not only resulted in, and the low strength of materials, poor heat resistance, recovery stress are small, it is slow to reply speed, also
Material glass transition temperature range is set to broaden so as to temperature sensitive property declines.And introduce particle, continuous fiber etc. and form shape
Shape memory composite material can improve mechanical strength, modulus, recovery stress etc., but the SME of meeting expendable material is such as broken
Strain, can recovery strain etc..
The content of the invention
It is a primary object of the present invention to provide a kind of rosin epoxy resin curing agent, its preparation method and application, with
Overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of rosin epoxy resin curing agent is provided in certain embodiments, and it is selected from structure shown in formula I
Compound:
Wherein, R is aliphatic segment.
Further, R is selected from comprising-(CH2)n- alkyl segment, n is the integer more than or equal to 2, preferably 2 or 3.
A kind of preparation method of rosin epoxy resin curing agent is provided in certain embodiments, and it includes:By propylene
The propylene of pimaric acid two mixes with the compound comprising amino and sulfydryl in the organic solvent containing light trigger, and makes to be formed
Mixed system reacted under ultraviolet light, it is then post-treated and obtain the rosin epoxy resin curing agent.
A kind of composition is provided in certain embodiments, and it includes described rosin epoxy resin curing agent and energy
The enough epoxy resin that solidfied material is cooperatively formed with the rosin epoxy resin curing agent.
The epoxy resin may be selected from but be not limited to bisphenol A epoxide resin, terephthalic acid (TPA) diglycidyl ether, acrylic acid
Any one or more in modified rosin base epoxy.
A kind of solidfied material is provided in certain embodiments, is mainly solidify to form by described composition.
A kind of preparation method of solidfied material is provided in certain embodiments, and it includes:Described composition is taken to exist successively
80~100 DEG C of solidifications 1~2h, 120~140 DEG C of solidifications 1~2h, 160~180 DEG C of 2~5h of solidification, obtain the solidfied material.
Purposes of the solidfied material as shape-memory material is additionally provided in certain embodiments.
Compared with prior art, advantages of the present invention includes:
(1) with bio-based materials rosin as initiation material, a kind of environmental protection, health has been obtained and preparation condition is simply biological
Based epoxy curing agent, wherein because raw material rosin acid includes hydrogen phenanthrene ring, making possess good power after the curing agent is cured
Performance and thermal property are learned, with good application prospect.
(2) preparation condition of rosin epoxy resin curing agent of the present invention is easy to implement, preparation technology environmental protection, manufacturing cost
It is cheap.
(3) present invention, for the deep processing of China's rosin resource provides new way, is conducive to renewable rosin as raw material
The economic worth of rosin is further played, and new raw material and new way have been opened up to prepare new curing agent;
(4) rosin epoxy resin curing agent of the present invention is applicable to shape-memory material field, such as the rosin based on as described in
The solidfied material of based epoxy curing agent can be used as shape-memory material, and it has good calorifics, mechanics and shape memory
Performance.
Brief description of the drawings
Fig. 1 is by obtaining the hydrogen nuclear magnetic resonance spectrogram of rosin epoxy resin curing agent in embodiment 1.
Specific embodiment
The invention mainly relates to a kind of rosin epoxy resin curing agent, its preparing raw material rosin acid system is biogenetic derivation,
And possess good performance by the solidfied material that the curing agent is formed.
One aspect of the present invention provides a kind of rosin epoxy resin curing agent, and it is selected from structure shown in formula I
Compound:
Wherein, R is aliphatic segment, it is preferred that R is selected from comprising-(CH2)n- alkyl segment, n is more than or equal to 2
Integer, preferably 2 or 3.
Another aspect of the present invention provides a kind of preparation method of rosin epoxy resin curing agent, and it includes:Will
The propylene of rosin acrylic acid two mixes with the compound comprising amino and sulfydryl in the organic solvent containing light trigger, and makes
The mixed system of formation reacts under ultraviolet light, then post-treated and obtain target product.
Among one more specific embodiment, the preparation method includes:Polymerization inhibitor is added by raw material of rosin acid
Hydroquinones and acrylic acid, rosin acrylic acid is obtained by the reaction of Diels-Alder, is then reacted using carboxyl and bromopropene
The propylene of rosin acrylic acid two is prepared, rosin epoxy resin curing agent is finally prepared using the reaction of double bond and sulfydryl.
Among one more specifically embodiment, the preparation method is comprised the following steps:
(1) preparation of rosin acrylic acid;
(2) preparation of the propylene of rosin acrylic acid two;
(3) preparation of rosin epoxy resin curing agent:By the propylene of rosin acrylic acid two with comprising amino and sulfydryl
Compound is added in the organic solvent containing light trigger, then ultraviolet light reaction.Reaction washs product after terminating,
Except solvent, target product is dried to obtain.
The compound comprising amino and sulfydryl is selected from NH2- R-SH or their hydrochloride compound, R for-
(CH2)n-, n is the positive integer more than or equal to 2, preferably 2 or 3.
Among some preferred embodiments, the propylene of the rosin acrylic acid two, contain the change of amino and sulfydryl simultaneously
Compound, the mass ratio of light trigger are:1:0.3~0.7:0.004~0.08.
Further, the organic solvent preferably from but be not limited to dimethylformamide, Isosorbide-5-Nitrae-dioxane, ethanol,
One or more in tetrahydrofuran.
Further, the light trigger preferably from but be not limited to benzoin dimethylether, camphorquinone, in benzophenone
It is a kind of.
Wherein, the consumption of light trigger can according to reaction material quantity adjustment, by can initiation reaction be defined, in order to
Preferably catalytic effect is played while economizing in raw materials, the consumption of light trigger is preferably the propylene quality of rosin acrylic acid two
0.4%~8%.
Among some preferred embodiments, described reaction condition is to irradiate 1~8h under ultraviolet light.
The rosin acrylic acid can be prepared using mode known to industry, the scheme as disclosed in using CN102977265A
Prepare.For example, used as one of preferred scheme, the preparation method of the rosin acrylic acid can include:Under protective atmosphere,
Rosin acid, acrylic acid and hydroquinone of polymerization retarder are mixed, 140~160 DEG C of 1~3h of reaction are heated to, is then heated to
170~200 DEG C of 4~15h of reaction, products therefrom ultrasonic dissolution is in ether, then adds it to relative to 2~6 times of bodies of ether
Precipitated in long-pending petroleum ether, be finally dried to obtain rosin acrylic acid.
More preferred, the mass ratio of the rosin acid, acrylic acid and hydroquinones three is:1:0.2~0.7:0.004
~0.04.
Further, one or more formation that the protective atmosphere can be selected in nitrogen, argon gas, helium etc., from
From the point of view of cost-effective, preferred nitrogen.
The propylene of the rosin acrylic acid two can also be prepared using mode known to industry, such as use CN102977265A
It is prepared by disclosed scheme.For example, used as one of preferred scheme, the preparation method of the propylene of the rosin acrylic acid two includes:
Rosin acrylic acid, bromopropene, acid binding agent potassium carbonate are added in acetone solvent, 12~24h of stirring reaction at 60~90 DEG C,
Products therefrom takes organic phase by washing, and then re-dry obtains the propylene of rosin acrylic acid two.
More preferred, the mass ratio between the rosin acrylic acid, bromopropene and potassium carbonate three is:1:1~2:0.5
~1.5.
An additional aspect of the present invention additionally provides the purposes of the rosin epoxy resin curing agent.
For example, providing a kind of composition in certain embodiments, it includes described rosin epoxy resin curing agent
And the epoxy resin of solidfied material can be cooperatively formed with the rosin epoxy resin curing agent.
The epoxy resin at least may be selected from bisphenol A epoxide resin, and terephthalic acid (TPA) diglycidyl ether is acrylic acid modified
Any one in rosin epoxy resin, but not limited to this.
Among one more preferred embodiment, the composition is made up of the raw material of following weight portion:
The weight portion of rosin epoxy resin curing agent 100;
The described weight portion of epoxy resin 90~160.
For example, additionally providing a kind of solidfied material in certain embodiments, mainly it is solidify to form by described composition.
For example, additionally providing a kind of method for preparing the solidfied material in certain embodiments, it includes:Take described group
Compound solidifies 1~2h, 120~140 DEG C of solidifications 1~2h, 160~180 DEG C of 2~5h of solidification at 80~100 DEG C successively, obtains described
Solidfied material.The solidfied material has preferable mechanics, calorifics and shape-memory properties.
Therefore, accordingly, purposes of the solidfied material as shape-memory material is additionally provided in certain embodiments.
Embodying feature of present invention will describe in detail in the following description with the exemplary embodiments of advantage.It should be understood that this
Invention can have various changes in different embodiments, and it is neither departed from the scope of the present invention, and it is therein explanation and
Diagram is treated as purposes of discussion in itself, and is not used to the limitation present invention.
Unless otherwise defined, all of technology and scientific terminology that this specification is used are led with technology of the invention is belonged to
The implication that the technical staff in domain is generally understood that is identical.It is specific that the term for being used in the description of the invention is intended merely to description
Embodiment purpose, it is not intended that in limitation the present invention.
Embodiment 1
(1) under nitrogen protection, by the inhibition of the rosin acid of 50 weight portions, the acrylic acid of 10 weight portions and 2 weight portions
Agent hydroquinones mixes, and is heated to 140 DEG C of reaction 2h, is then heated to 170 DEG C of reaction 15h, and products therefrom ultrasonic dissolution exists
In ether, then add it to be precipitated relative in 6 times of petroleum ethers of volume of ether, be finally dried to obtain rosin acrylic acid.
(2) the acid binding agent potassium carbonate of the rosin acrylic acid of 30 weight portions, the bromopropene of 60 weight portions, 30 weight portions is added
To in acetone solvent, stirring reaction 12h at 80 DEG C, products therefrom takes organic phase by washing, and then re-dry obtains propylene sea
Sour two propylene of pine.
(3) propylene of rosin acrylic acid two of 10 weight portions is added to the alpha-mercapto ethylamine hydrochloride of 5 weight portions and is contained
Have in the DMF solvent of light trigger benzoin dimethylether of 0.4 weight portion, then ultraviolet light is reacted
4h.Reaction washs product after terminating, and except solvent, is dried to obtain rosin epoxy resin curing agent, the rosin epoxy resin
The Structural Identification result of curing agent is as shown in figure 1, its specific data is as follows:1H-NMR(CDCl3, ppm):0.65,1.13,1.04,
1.26~2.03,2.52,3.70,4.04~4.15,5.32.Show that above-mentioned rosin epoxy resin has structure shown in formula II:
The bisphenol A epoxide resin of the rosin epoxy resin curing agent of obtained 100 weight portion and 100 weight portions is abundant
Mixing, successively in 100 DEG C of curing agent 2h, 130 DEG C of solidification 2h, obtains solidfied material, the bending die of the solidfied material after 180 DEG C of solidification 2h
It is 2460MPa to measure, and bending strength is 100MPa, and stretch modulus is 3144MPa, and tensile strength is 72MPa, shape memory fixed rate
It is 98.8%, shape recovery rate is 99.0%, when thermal weight loss quality is 5%, corresponding decomposition temperature is at 314 DEG C.
Embodiment 2
(1) under nitrogen protection, by the inhibition of the rosin acid of 50 weight portions, the acrylic acid of 35 weight portions and 1 weight portion
Agent hydroquinones mixes, and is heated to 160 DEG C of reaction 1h, is then heated to 200 DEG C of reaction 4h, and products therefrom ultrasonic dissolution is in second
In ether, then add it to be precipitated relative in 4 times of petroleum ethers of volume of ether, be finally dried to obtain rosin acrylic acid.
(2) the acid binding agent potassium carbonate of the rosin acrylic acid of 30 weight portions, the bromopropene of 30 weight portions, 15 weight portions is added
To in acetone solvent, stirring reaction 18h at 70 DEG C, products therefrom takes organic phase by washing, and then re-dry obtains propylene sea
Sour two propylene of pine.
(3) the alpha-mercapto ethamine of the propylene of rosin acrylic acid two of 10 weight portions and 3 weight portions is added to and contains 0.04
In the Isosorbide-5-Nitrae-dioxane/alcohol solvent of the light trigger benzophenone of weight portion, then ultraviolet light reacts 8h.Reaction knot
Product is washed after beam, except solvent, is dried to obtain rosin epoxy resin curing agent, its Structural Identification data is as follows:1H-NMR
(CDCl3, ppm):0.65,1.13,1.04,1.26~2.03,2.52,3.70,4.04~4.15,5.32, it is consistent with Fig. 1.
Show the rosin epoxy resin curing agent structure as shown in formula II.
The terephthalic acid (TPA) two of the rosin epoxy resin curing agent of obtained 100 weight portion and 90 weight portions is shunk sweet
Oily ether is sufficiently mixed, and in 80 DEG C of curing agent 2h, obtains Abietyl-containing epoxy resin after 120 DEG C of solidification 2h, and 160 DEG C of solidification 5h and consolidates
The solidfied material of agent.The bending modulus of the solidfied material of the Abietyl-containing epoxy curing agent of gained is 2448MPa, bending strength
It is 98MPa, stretch modulus is 3136MPa, and tensile strength is 70MPa, and shape memory fixed rate is 98.4%, and shape recovery rate is
98.5%, when thermal weight loss quality is 5%, corresponding decomposition temperature is at 310 DEG C.
Embodiment 3
(1) under nitrogen protection, by the resistance of the rosin acid of 50 weight portions, the acrylic acid of 25 weight portions and 0.2 weight portion
Poly- agent hydroquinones mixing, is heated to 150 DEG C of reaction 2h, is then heated to 180 DEG C of reaction 9h, and products therefrom ultrasonic dissolution exists
In ether, then add it to be precipitated relative in 2 times of petroleum ethers of volume of ether, be finally dried to obtain rosin acrylic acid.
(2) the acid binding agent potassium carbonate of the rosin acrylic acid of 30 weight portions, the bromopropene of 45 weight portions, 45 weight portions is added
To in acetone solvent, stirring reaction 12h at 90 DEG C, products therefrom takes organic phase by washing, and then re-dry obtains propylene sea
Sour two propylene of pine.
(3) by the propylene of rosin acrylic acid two of 10 weight portions and the 3- sulfydryl -1- propylamine of 7 weight portions be added to containing
In the tetrahydrofuran solvent of the light trigger camphorquinone of 0.8 weight portion, then ultraviolet light reacts 1h.Reaction will be produced after terminating
Thing is washed, and except solvent, is dried to obtain rosin epoxy resin curing agent, and its Structural Identification data is as follows:1H-NMR(CDCl3,
ppm):0.65,1.13,1.04,1.26~2.03,2.52~2.63,2.89,4.04~4.15,5.32.Show above-mentioned abietyl
Epoxy resin has structure shown in formula III:
By the rosin epoxy resin curing agent of obtained 100 weight portion and the acrylic acid modified rosin base of 160 weight portions
Epoxy resin is sufficiently mixed, and in 90 DEG C of curing agent 2h, Abietyl-containing asphalt mixtures modified by epoxy resin is obtained after 140 DEG C of solidification 1h, and 170 DEG C of solidification 4h
The solidfied material of fat curing agent.The bending modulus of the solidfied material of the Abietyl-containing epoxy curing agent of gained is 2350MPa, bending
Intensity is 90MPa, and stretch modulus is 3200MPa, and tensile strength is 70MPa, and shape memory fixed rate is 98%, shape recovery rate
It is 99%, when thermal weight loss quality is 5%, corresponding decomposition temperature is at 321 DEG C.
Embodiment 4
(1) under nitrogen protection, by the resistance of the rosin acid of 50 weight portions, the acrylic acid of 20 weight portions and 0.5 weight portion
Poly- agent hydroquinones mixing, is heated to 145 DEG C of reaction 2h, is then heated to 190 DEG C of reaction 6h, and products therefrom ultrasonic dissolution exists
In ether, then add it to be precipitated relative in 5 times of petroleum ethers of volume of ether, be finally dried to obtain rosin acrylic acid.
(2) the acid binding agent potassium carbonate of the rosin acrylic acid of 30 weight portions, the bromopropene of 39 weight portions, 21 weight portions is added
To in acetone solvent, stirring reaction 20h at 70 DEG C, products therefrom takes organic phase by washing, and then re-dry obtains propylene sea
Sour two propylene of pine.
(3) propylene of rosin acrylic acid two of 10 weight portions is added to the alpha-mercapto ethylamine hydrochloride of 4 weight portions and is contained
Have in the Isosorbide-5-Nitrae-dioxane solvent of light trigger benzoin dimethylether of 0.2 weight portion, then ultraviolet light reacts 5h.Instead
Product is washed after should terminating, except solvent, is dried to obtain rosin epoxy resin curing agent, its Structural Identification result such as Fig. 1 institutes
Show, specific data are:1H-NMR(CDCl3, ppm):0.65,1.13,1.04,1.26~2.03,2.52,3.70,4.04~
4.15,5.32, it is consistent with Fig. 1.Show above-mentioned rosin epoxy resin curing agent structure as shown in formula II.
The bisphenol A epoxide resin of the rosin epoxy resin curing agent of obtained 100 weight portion and 110 weight portions is abundant
Mixing, in 85 DEG C of curing agent 2h, consolidating for Abietyl-containing epoxy curing agent is obtained after 125 DEG C of solidification 2h, and 165 DEG C of solidification 4h
Compound.The bending modulus of the solidfied material of the Abietyl-containing epoxy curing agent of gained is 2438MPa, and bending strength is 96MPa,
Stretch modulus is 3130MPa, and tensile strength is 71MPa, and shape memory fixed rate is 98.2%, and shape recovery rate is 98.7%,
When thermal weight loss quality is 5%, corresponding decomposition temperature is at 311 DEG C.
Embodiment 5
(1) under nitrogen protection, by the resistance of the rosin acid of 50 weight portions, the acrylic acid of 30 weight portions and 1.5 weight portions
Poly- agent hydroquinones mixing, is heated to 155 reaction 1h, is then heated to 185 DEG C of reaction 8h, and products therefrom ultrasonic dissolution is in second
In ether, then add it to be precipitated relative in 3 times of petroleum ethers of volume of ether, be finally dried to obtain rosin acrylic acid.
(2) the acid binding agent potassium carbonate of the rosin acrylic acid of 30 weight portions, the bromopropene of 51 weight portions, 39 weight portions is added
To in acetone solvent, stirring reaction 19h at 75 DEG C, products therefrom takes organic phase by washing, and then re-dry obtains propylene sea
Sour two propylene of pine.
(3) by the propylene of rosin acrylic acid two of 10 weight portions and the 3- sulfydryl -1- propylamine of 6 weight portions be added to containing
In the DMF/alcohol solvent of the light trigger benzophenone of 0.6 weight portion, then ultraviolet light reaction
3h.Reaction washs product after terminating, and except solvent, is dried to obtain rosin epoxy resin curing agent, and its Structural Identification result is such as
Under:1H-NMR(CDCl3, ppm):0.65,1.13,1.04,1.26~2.03,2.52~2.63,2.89,4.04~4.15,
5.32.Show above-mentioned rosin epoxy resin curing agent structure as shown in formula III.
The bisphenol A epoxide resin of the rosin epoxy resin curing agent of obtained 100 weight portion and 130 weight portions is abundant
Mixing, in 95 DEG C of curing agent 2h, consolidating for Abietyl-containing epoxy curing agent is obtained after 135 DEG C of solidification 1h, and 175 DEG C of solidification 4h
Compound.The bending modulus of the solidfied material of the Abietyl-containing epoxy curing agent of gained is 2252MPa, and bending strength is 86MPa,
Stretch modulus is 3000MPa, and tensile strength is 64MPa, and shape memory fixed rate is 99.1%, and shape recovery rate is 98.3%,
When thermal weight loss quality is 5%, corresponding decomposition temperature is at 307 DEG C.
It should be understood that implementation method described in the invention is merely for exemplary purpose, and it is not used to the limitation present invention
Protection domain, those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus,
The invention is not restricted to above-mentioned implementation method, and only it is defined by the claims.
Claims (18)
1. a kind of rosin epoxy resin curing agent, it is characterised in that it is selected from the compound with structure shown in formula I:
Wherein, R is aliphatic segment.
2. rosin epoxy resin curing agent as claimed in claim 1, it is characterised in that:R is selected from comprising-(CH2)n- alkyl
Segment, n is the integer more than or equal to 2.
3. rosin epoxy resin curing agent as claimed in claim 2, it is characterised in that:N is 2 or 3.
4. a kind of preparation method of rosin epoxy resin curing agent, it is characterised in that including:By the propylene of rosin acrylic acid two
Mix in the organic solvent containing light trigger with the compound comprising amino and sulfydryl, and make the mixed system to be formed in purple
Reacted under outer light irradiation, then it is post-treated and obtain the rosin epoxy resin curing agent.
5. preparation method as claimed in claim 4, it is characterised in that:The compound comprising amino and sulfydryl is selected from NH2-
R-SH and/or NH2The hydrochloride compound of-R-SH, R is comprising-(CH2)n- alkyl segment, n is whole more than or equal to 2
Number.
6. preparation method as claimed in claim 5, it is characterised in that:N is 2 or 3.
7. preparation method as claimed in claim 4, it is characterised in that:The light trigger includes benzoin dimethylether, camphor
Any one in quinone and benzophenone or two or more combinations.
8. preparation method as claimed in claim 4, it is characterised in that:The organic solvent includes DMF,
Isosorbide-5-Nitrae-dioxane, ethanol, any one in tetrahydrofuran or two or more combinations.
9. preparation method as claimed in claim 4, it is characterised in that:The propylene of the rosin acrylic acid two, comprising amino and
The compound of sulfydryl is 1 with the mass ratio of light trigger:0.3~0.7:0.004~0.08.
10. the preparation method of rosin epoxy resin curing agent as claimed in claim 4, it is characterised in that including:Will be described
Mixed system 1~8h of room temperature reaction under ultraviolet light.
The preparation method of 11. rosin epoxy resin curing agent as claimed in claim 4, it is characterised in that the post processing
Including being washed to product after the completion of reaction, except solvent, behaviour that is dry and obtaining the rosin epoxy resin curing agent
Make.
The preparation method of 12. rosin epoxy resin curing agent as claimed in claim 4, it is characterised in that including:In protection
Property atmosphere under, by rosin acid, acrylic acid and hydroquinone of polymerization retarder mix, be heated to 140~160 DEG C reaction 1~3h, then
170~200 DEG C of 4~15h of reaction are heated to, products therefrom is dissolved in ether, is then added to relative to 2~6 times of bodies of ether
Precipitated in long-pending petroleum ether, rosin acrylic acid is dried to obtain thereafter, the rosin acrylic acid is obtained using rosin acrylic acid afterwards
Two propylenes.
13. a kind of compositions, it is characterised in that including the rosin epoxy resin solidification as any one of claim 1-3
Agent and the epoxy resin of solidfied material can be cooperatively formed with the rosin epoxy resin curing agent.
14. compositions according to claim 13, it is characterised in that:The composition includes the pine described in 100 weight portions
Epoxy resin described in perfume base epoxy curing agent and 90~160 weight portions.
15. composition according to claim 13 or 14, it is characterised in that:The epoxy resin includes bisphenol-A epoxy tree
Fat, terephthalic acid (TPA) diglycidyl ether, any one in acrylic acid modified rosin base epoxy or two or more groups
Close.
A kind of 16. solidfied materials, mainly the composition as described in claim 13,14 or 15 solidify to form.
A kind of 17. preparation methods of solidfied material, it is characterised in that including:Take composition described in claim 13,14 or 15 according to
It is secondary to solidify 1~2h, 120~140 DEG C of solidifications 1~2h, 160~180 DEG C of 2~5h of solidification at 80~100 DEG C, obtain the solidification
Thing.
18. solidfied materials as claimed in claim 16 as shape-memory material purposes.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510845395.XA CN105482078B (en) | 2015-11-27 | 2015-11-27 | Rosin epoxy resin curing agent, its preparation method and application |
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CN107418491A (en) * | 2017-09-21 | 2017-12-01 | 通号工程局集团有限公司 | A kind of conducting resinl and preparation method thereof |
CN109694461A (en) * | 2017-10-20 | 2019-04-30 | 中国林业科学研究院林产化学工业研究所 | It is a kind of based on anacardol, to the preparation method of the shape memory epoxy resin material of Meng's alkane diamines and furfural |
CN108409942A (en) * | 2018-04-13 | 2018-08-17 | 西北农林科技大学 | A kind of rosin epoxy resin nanocomposite preparation method |
CN109180542B (en) * | 2018-06-29 | 2019-08-13 | 华南农业大学 | A kind of preparation method and application of galla turcica acidic group mercaptan and its shape-memory polymer |
CN110643019B (en) * | 2019-10-11 | 2022-03-01 | 陕西科技大学 | Eugenol-based epoxy resin curing agent based on mercapto-alkene click reaction, preparation method and application |
CN111484530B (en) * | 2020-04-22 | 2022-07-26 | 中航复材(北京)科技有限公司 | Rosin-based reactive flame-retardant curing agent and preparation method thereof |
CN111530099A (en) * | 2020-05-19 | 2020-08-14 | 临沂大学 | Manual toy product with shape memory function and use method |
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