CN110183737A - A kind of impact resistance high-stability type material - Google Patents
A kind of impact resistance high-stability type material Download PDFInfo
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- CN110183737A CN110183737A CN201910416552.3A CN201910416552A CN110183737A CN 110183737 A CN110183737 A CN 110183737A CN 201910416552 A CN201910416552 A CN 201910416552A CN 110183737 A CN110183737 A CN 110183737A
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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
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/288—Alkyl ethers substituted with nitrogen-containing radicals
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of impact resistance high-stability type materials, belong to macromolecule field of fine chemical.The present invention carries out graft copolymerization to polylactic acid to maleic anhydride, and intermolecular gap is small in Blending Processes, in conjunction with closer, improves interface cracking resistance, melt pelletization process can reduce intermolecular gap, further increase dimensional stability and impact resistance；Starch is modified using propylene oxide as etherifying agent, form a kind of aqueous gel, moisture sensitivity when material is blended can be substantially reduced, collaboration promotes dimensional stability, it is cation-modified to microcrystalline cellulose progress using 2,3- epoxypropyltrimethylchloride chloride, improve the dispersibility of compound system and the connecting forces of inside, dispersion uneven problem occurs when avoiding being blended with other ingredients such as made compound high impact materials, so that the stability of this size and impact resistance are improved.The present invention solves the problems, such as to commonly use high impact material dimensional stability at present and impact resistance is bad.
Description
Technical field
The present invention relates to a kind of impact resistance high-stability type materials, belong to macromolecule technical field of fine.
Background technique
It is used in general, the participant of movement (for example, football, rugby, baseball, lacrosse, hockey etc.) dresses protection
Tool is to be buffered in the impact force being often subject to during those activities.In recent years, the brute force attack during such contact movement
Danger have become focal issue.The danger of these impacts can be weakened by effectively buffering the impact force that participant is subject to
Or it minimizes.For example, referred to as commotio cordis (commotio cordis) by movement in chest impact caused by it is sudden cardiac sudden
It extremely, is worried in the movement for have missile.Baseball, lacrosse and hockey are that three kinds of common fortune of commotio cordis occur
It is dynamic.More alarmingly, commotio cordis still occurs because of wall of the chest impact although moving participant and having dressed chest protector.In fact,
The commotio cordis event of potential one third occurs on the individual that wearing has chest protector in the above competitive sport.Therefore, it is necessary to
Adequately protect sportsman from commotio cordis risk improved high impact material.Presently available surge guard material tends to point
For two classes, that is, wear may uncomfortable firm shell (such as knee or ancon fender) or provide weak level of protection and
Usually wear uncomfortable foam pad (such as liner of clothing).Accordingly, it has been suggested that having both protection and the foam pad of firm shell
Energy absorbing material flexible.Energy absorbing material, which exists, to be widely applied, such as such as with the movement for being potentially dangerous
By motorcycle, it skis, skate, the protective garment form of slide plate skating and snowboarding, and as protective package material.It is logical
Often, energy absorbing material is modelled in flakes, then can be further processed into partly or entirely by sheet material formed at shape
Product.Sheet material can be formed by energy absorbing material itself or piece can be by the substrate such as fabric or foam that are impregnated by energy absorbing material
It is formed.However, it is possible for for example being provided by moulding or being formed in situ method as the energy absorbing material of preforming article
's.Epoxy resin has excellent physical mechanical and electrical insulation capability, and the adhesive property with a variety of materials, also, it makes
Not available for being other thermosetting plasticses with the flexibility of technique.Therefore, coating, composite material, casting is made in epoxy resin
Material, adhesive, moulding material and injecting forming material, are widely used in every field.And existing for epoxy resin
Defect essentially consists in two aspects, is on the one hand that its toughness is inadequate, second aspect is that its temperature capacity needs to be further increased.
Thus, the modification work to epoxy resin is mainly also to carry out for the two aspects.The method of epoxy resin roughening is mainly adopted
Means include: second phase particles toughening, inierpeneirating network structure toughening, chemical modification method toughening, wherein being grafted poly- silicon oxygen
Alkane is a kind of relatively effective method.And improving epoxy resin heat resistance method then mainly includes addition fire resistant resin, or
By introducing high temperature resistant group or high temperature resistant compound etc..Currently, people, which are modified it also, cannot concurrently reach high temperature resistant and tough
The relatively good effect of property.In general, the general main chain of the preferable group of the toughness of access contains carbon-carbon double bond, sulphur oxygen key, carbon oxygen
Key or silicon oxygen bond, and the thermal stability of carbon-carbon double bond, sulphur oxygen key and carbon-oxygen bond is poor, only silicon oxygen bond is comparatively steady to heat
It is fixed.But since the compatibility of polysiloxanes and epoxy resin is poor, thus the method for conventional graft polysiloxane is to toughness
Raising it is limited, cause high impact material dimensional stability and impact resistance bad.
Summary of the invention
The technical problems to be solved by the invention: for common high impact material dimensional stability and impact resistance at present
Bad problem provides a kind of impact resistance high-stability type material.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of impact resistance high-stability type material, according to the mass fraction, including following component: 2 ~ 5 parts of zinc stearates, 3 ~ 7 parts of asphalt mixtures modified by epoxy resin
Rouge, 1 ~ 4 part of antioxidant, 2 ~ 5 parts of plasticizer, 2 ~ 5 parts of auxiliary materials, further includes: 25 ~ 50 parts of compound impact resistance base-materials, 12 ~ 20 parts it is pre-
Handle microcrystalline cellulose.
The preparation method of the compound impact resistance base-material, includes the following steps:
(1) in 26 ~ 32 DEG C, 1:2 ~ 4 take polylactic acid, reagent A to be mixed in mass ratio, are warming up to 48 ~ 60 DEG C, and polylactic acid is added
The maleic anhydride of quality 25 ~ 40%, the sodium peroxydisulfate of polylactic acid quality 4 ~ 8% are mixed, and obtain reaction material, take reaction material by quality
Dehydrated alcohol mixing is added than 1:12 ~ 20, is stored at room temperature, filters, filter residue is taken to be washed with ethanol solution, it is dry, obtain dried object；
(2) 1:20 ~ 40 take konjaku, water to be mixed in mass ratio, and the sodium metaperiodate that konjaku quality 1 ~ 4% is added is mixed, room
Temperature is stood, and must be aoxidized konjaku material, according to parts by weight, be taken 20 ~ 40 parts of dried objects, 30 ~ 50 parts of water, the chloro- 2- hydroxypropyl of 10 ~ 15 parts of 3-
Base trimethyl ammonium chloride, 7 ~ 12 parts of oxidation konjaku material, 2 ~ 5 parts of hydroxyapatites, 7 ~ 12 parts of pretreated starch, first take the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride, water, oxidation konjaku material, pretreated starch mixing, adjust pH value, hydroxyapatite, drying are added
Object mixing, stirs in 70 ~ 85 DEG C, obtains base-material, takes base-material rotary evaporation, is concentrated in vacuo to get compound impact resistance base-material.
Reagent A in the step (1): 3 ~ 6:1 in mass ratio takes toluene, methylene chloride mixing to get reagent A.
Pretreated starch in the step (2): take starch 4 ~ 8:1:25 in mass ratio ~ 35 that sodium sulphate, NaOH is added molten
Liquid is mixed, and the propylene oxide mixing of starch quality 6 ~ 10% is added, adjusts pH, is stored at room temperature, filter, take filtration cakes torrefaction, i.e.,
Obtain pretreated starch.
The preparation of the pretreatment microcrystalline cellulose: in 25 ~ 35 DEG C, take microcrystalline cellulose 1:12 in mass ratio ~ 20 that examination is added
Agent B is mixed, and obtains mixed object, and mixed object 1:8 ~ 15 in mass ratio plus water mixing, centrifugation is taken to take supernatant to dialyse, obtain dialysate, take
Dialysate rotary evaporation is concentrated under reduced pressure, obtains concentrate, takes concentrate 1:4 in mass ratio ~ 8 that organic reagent mixing is added, in 50 ~
65 DEG C, stirring obtains mixing, takes mixing 30 ~ 50:0.1 in mass ratio ~ 0.3:2 that sodium hydroxide, 2,3- epoxy is added
Ammonium chloride mixes, and reacts under the conditions of 60 ~ 75 DEG C of Yu Wendu, 3.2 ~ 4.8MPa of pressure, pressure release obtains reaction material, takes reaction material by matter
Amount is added ethanol solution than 1:8 ~ 12 and is mixed, centrifugation, takes the freeze-drying of centrifugation object to get pretreatment microcrystalline cellulose.
The organic reagent: 4 ~ 8:1 takes dimethyl sulfoxide, petroleum ether mixing to get organic reagent by volume.
The reagent B: 6 ~ 10:1 in mass ratio takes sulfuric acid solution, NH4Cl mixes to get reagent B.
The plasticizer: 5 ~ 8:3 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticising
Agent.
The antioxidant: 3 ~ 6:1 in mass ratio takes double stearyl alcohol pentaerythritol diphosphites, N- phenyl-β-
Naphthylamines mixes to get antioxidant.
The auxiliary material: 1:2 ~ 4:0.1 in mass ratio takes polytetrafluoroethylene (PTFE), hydroxyethyl cellulose, dopamine mixing to get auxiliary
Material.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention using maleic anhydride, polylactic acid be raw material carry out graft copolymerization, then with pretreated starch, aoxidize konjaku flour
Equal ingredients are blended, so that having better plasticity after its blend, so that mixture faying face keeps smooth, can make
Polydactyl acid and other intermolecular gaps are smaller, in conjunction with closer, raising interface cracking resistance, thus improve ontology
Stability, and a small amount of dopamine being added can further improve film forming in the blending process, assist the epoxy resin of addition
Also can reinforced cementitious power, and may make up absorption or bridging effect, so that polydactyl acid ingredient, pretreatment microcrystalline cellulose, pre-
It handles and occurs closely to combine between starch, constitute multi-level cross-linked structure network, and during melt pelletization, it can reduce
Intermolecular gap further increases dimensional stability and impact resistance, improves the using effect of this material；
(2) present invention is modified starch using propylene oxide as etherifying agent, with the konjaku meal component matter through sodium periodate oxidation
When blending, there is good swellability, form a kind of high stability aqueous gel, the humidity that can be substantially reduced when material is blended is quick
Perception, collaboration promote dimensional stability, can form good boundary therewith in conjunction with microcrystalline cellulose surface functional group abundant
Face compatibility and adhesiveness carry out acidleach to microcrystalline cellulose, generate part nano micro crystal cellulose, compare table with biggish
Area, higher crystallinity and intensity reuse 2,3- epoxypropyltrimethylchloride chloride and carry out cation to microcrystalline cellulose
It is modified, can not only make microcrystalline cellulose that hydrophobicity be presented so that particle formed in water suspension into and constitute electric double layer, mention
High intergranular repulsive force, improves the dispersibility of compound system and the connecting forces of inside, avoids and made compound impact resistance
Dispersion uneven problem occurs when other ingredients such as material are blended, external stress can be dispersed well, so that size of the invention
Stability and impact resistance are improved；
(3) present invention carries out graft copolymerization to macromolecular substances, and polydactyl acid and other intermolecular gaps can be made smaller,
In conjunction with closer, raising interface cracking resistance, thus the stability of ontology is improved, assists the epoxy resin of addition that can also add
Strong cohesive force, and may make up absorption or bridging effect, so that polydactyl acid ingredient, pretreatment microcrystalline cellulose, pretreated starch
Between occur closely to combine, constitute multi-level cross-linked structure network, and during melt pelletization, can reduce intermolecular
Gap improves dimensional stability and impact resistance, improves the using effect of this material.
Specific embodiment
Pretreated starch: take the NaOH that sodium sulphate is added in starch 4 ~ 8:1:25 in mass ratio ~ 35, mass fraction is 12% molten
Liquid mixing is added the propylene oxide mixing of starch quality 6 ~ 10%, is used concentration with 450 ~ 700r/min, 35 ~ 60min of magnetic agitation
The HCl solution of 0.01mol/L adjusts pH to 6.7 ~ 7.2, is stored at room temperature 2 ~ 4h, filters, take filter cake in 60 ~ 80 DEG C of oven dryings extremely
Constant weight is to get pretreated starch.
Reagent A: 3 ~ 6:1 in mass ratio takes toluene, methylene chloride mixing to get reagent A.
Reagent B: 6 ~ 10:1 in mass ratio takes the sulfuric acid solution that mass fraction is 15%, NH4Cl mixes to get reagent B.
Organic reagent: 4 ~ 8:1 takes dimethyl sulfoxide, petroleum ether mixing to get organic reagent by volume.
Auxiliary material: 1:2 ~ 4:0.1 in mass ratio takes polytetrafluoroethylene (PTFE), hydroxyethyl cellulose, dopamine mixing to get auxiliary material.
Antioxidant: 3 ~ 6:1 in mass ratio takes double stearyl alcohol pentaerythritol diphosphites, N- phenyl-β-naphthylamine
Mixing is to get antioxidant.
Plasticizer: 5 ~ 8:3 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
The preparation method of compound impact resistance base-material, includes the following steps:
(1) in 26 ~ 32 DEG C of water-bath, 1:2 ~ 4 take polylactic acid, reagent A mixing in mass ratio, with 500 ~ 800r/min magnetic agitation 40
~ 60min is warming up to 48 ~ 60 DEG C, and the maleic anhydride of polylactic acid quality 25 ~ 40%, the sodium peroxydisulfate of polylactic acid quality 4 ~ 8% is added
Mixing, with 600 ~ 900r/min, 45 ~ 65min of magnetic agitation, obtains reaction material, takes reaction material 1:12 in mass ratio ~ 20 to be added anhydrous
Ethyl alcohol mixing, is stored at room temperature 2 ~ 4h, filters, after taking filter residue to wash 2 ~ 4 times with the ethanol solution that volume fraction is 70%, move to 55 ~
80 DEG C of 3 ~ 5h of oven drying, obtain dried object；
(2) 1:20 ~ 40 take konjaku, water that 20 ~ 35min is mixed in reaction kettle in mass ratio, and the height of konjaku quality 1 ~ 4% is added
Sodium iodate is mixed, and is stored at room temperature 2 ~ 4h, must aoxidize konjaku material, according to parts by weight, takes 20 ~ 40 parts of dried objects, 30 ~ 50 parts
Water, 10 ~ 15 parts of 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 7 ~ 12 parts of oxidation konjaku material, 2 ~ 5 parts of hydroxyapatites, 7 ~ 12 parts it is pre-
Starch is handled, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, water, oxidation konjaku material, pretreated starch is first taken to mix in reaction kettle,
PH value is adjusted to 7.4 ~ 8.2 with the NaOH solution that mass fraction is 12%, hydroxyapatite, dried object mixing is added, in 70 ~ 85
DEG C with 450 ~ 800r/min, 1 ~ 3h of magnetic agitation, base-material is obtained, takes base-material in 60 ~ 80 DEG C of rotary evaporations, is concentrated in vacuo to constant weight, i.e.,
Obtain compound impact resistance base-material.
It pre-processes the preparation of microcrystalline cellulose: in 25 ~ 35 DEG C, taking microcrystalline cellulose 1:12 in mass ratio ~ 20 that reagent B is added mixed
It closes, with 350 ~ 550r/min, 1 ~ 3h of magnetic agitation, obtains mixed object, take mixed object 1:8 ~ 15 in mass ratio plus water mixing, move to centrifuge
It is centrifuged 8 ~ 15min with 3000 ~ 4000r/min, takes supernatant to dialyse 2 ~ 4 days, obtains dialysate, dialysate is taken to rotate in 65 ~ 85 DEG C
Evaporation, is concentrated under reduced pressure into constant weight, obtains concentrate, takes concentrate 1:4 in mass ratio ~ 8 that organic reagent mixing is added, in 50 ~ 65 DEG C,
Stir 25 ~ 50min with 500 ~ 800r/min, obtain mixing, take mixing 30 ~ 50:0.1 in mass ratio ~ 0.3:2 be added sodium hydroxide,
2,3- epoxypropyltrimethylchloride chlorides mix, and 1 ~ 3h is reacted under the conditions of 60 ~ 75 DEG C of Yu Wendu, 3.2 ~ 4.8MPa of pressure, natural
Pressure release obtains reaction material, takes reaction material 1:8 in mass ratio ~ 12 that the ethanol solution mixing that volume fraction is 70% is added and stir to normal pressure
It mixes, 7 ~ 13min is centrifuged with 3000 ~ 4000r/min, take centrifugation object micro- to get pre-processing in the dry 4 ~ 8h of -40 DEG C of freeze driers
Crystal fiber.
A kind of impact resistance high-stability type material, according to the mass fraction, including following component: 2 ~ 5 parts of zinc stearates, 3 ~ 7 parts of rings
Oxygen resin, 1 ~ 4 part of antioxidant, 2 ~ 5 parts of plasticizer, 2 ~ 5 parts of auxiliary materials, 25 ~ 50 parts of compound impact resistance base-materials, 12 ~ 20 parts of pre- places
Manage microcrystalline cellulose.
A kind of preparation method of impact resistance high-stability type material, includes the following steps:
(1) according to the mass fraction, 2 ~ 5 parts of zinc stearates, 3 ~ 7 parts of epoxy resin, 1 ~ 4 part of antioxidant, 2 ~ 5 parts of plasticizer, 2 are taken
~ 5 parts of auxiliary materials, 25 ~ 50 parts of compound impact resistance base-materials, 12 ~ 20 parts of pretreatment microcrystalline celluloses；
(2) prior to 40 ~ 60 DEG C, zinc stearate, epoxy resin, antioxidant, compound impact resistance base-material is taken to mix in batch mixer, with
500 ~ 800r/min, 35 ~ 60min of magnetic agitation is warming up to 90 ~ 110 DEG C, and it is mixed that pretreatment microcrystalline cellulose, plasticizer, auxiliary material is added
It closes, with 1000 ~ 1500r/min, 1 ~ 3h of magnetic agitation, obtains mixed material, mixed material is put into twin-screw extruder, in 170 ~ 200
DEG C melting extrusion, cooled to room temperature is to get impact resistance high-stability type material.
Embodiment 1
Pretreated starch: taking the NaOH solution that sodium sulphate is added in starch 4:1:25 in mass ratio, mass fraction is 12% to mix, with
The propylene oxide mixing of starch quality 6% is added, with the HCl solution tune of concentration 0.01mol/L in 450r/min magnetic agitation 35min
Save pH to 6.7, be stored at room temperature 2h, filter, take filter cake in 60 DEG C of oven dryings to constant weight to get pretreated starch.
Reagent A: 3:1 in mass ratio takes toluene, methylene chloride mixing to get reagent A.
Reagent B: 6:1 in mass ratio takes the sulfuric acid solution that mass fraction is 15%, NH4Cl mixes to get reagent B.
Organic reagent: 4:1 takes dimethyl sulfoxide, petroleum ether mixing to get organic reagent by volume.
Auxiliary material: 1:2:0.1 in mass ratio takes polytetrafluoroethylene (PTFE), hydroxyethyl cellulose, dopamine mixing to get auxiliary material.
Antioxidant: 3:1 in mass ratio takes double stearyl alcohol pentaerythritol diphosphites, N- phenyl-β-naphthylamine mixed
It closes to get antioxidant.
Plasticizer: 5:3 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
The preparation method of compound impact resistance base-material, includes the following steps:
(1) in 26 DEG C of water-bath, 1:2 in mass ratio takes polylactic acid, reagent A mixing, with 500r/min magnetic agitation 40min, heating
To 48 DEG C, the maleic anhydride of polylactic acid quality 25%, the sodium peroxydisulfate mixing of polylactic acid quality 4% is added, with 600r/min magnetic force
45min is stirred, reaction material is obtained, takes reaction material 1:12 in mass ratio that dehydrated alcohol mixing is added, is stored at room temperature 2h, filter, take filter
After slag washs 2 times with the ethanol solution that volume fraction is 70%, 55 DEG C of oven drying 3h are moved to, dried object is obtained；
(2) 1:20 in mass ratio takes konjaku, water that 20min is mixed in reaction kettle, and the sodium metaperiodate that konjaku quality 1% is added is mixed
Stirring is closed, 2h is stored at room temperature, konjaku material must be aoxidized, according to parts by weight, take 20 parts of dried objects, 30 parts of water, the chloro- 2- hydroxyl of 10 parts of 3-
Hydroxypropyltrimonium chloride, 7 parts of oxidation konjaku material, 2 parts of hydroxyapatites, 7 parts of pretreated starch, first take the chloro- 2- hydroxypropyl of 3-
Trimethyl ammonium chloride, water, oxidation konjaku material, pretreated starch are mixed in reaction kettle, the NaOH solution tune for being 12% with mass fraction
PH value is saved to 7.4, hydroxyapatite, dried object mixing is added, in 70 DEG C with 450r/min magnetic agitation 1h, obtains base-material, takes base
Expect to be concentrated in vacuo to constant weight in 60 DEG C of rotary evaporations to get compound impact resistance base-material.
It pre-processes the preparation of microcrystalline cellulose: in 25 DEG C, taking microcrystalline cellulose 1:12 in mass ratio that reagent B mixing is added, with
350r/min magnetic agitation 1h, obtains mixed object, takes mixed object 1:8 in mass ratio that water is added to mix, moves to centrifuge and be centrifuged with 3000r/min
8min takes supernatant to dialyse 2 days, obtains dialysate, take dialysate in 65 DEG C of rotary evaporations, be concentrated under reduced pressure into constant weight, obtain concentrate,
It takes concentrate 1:4 in mass ratio that organic reagent mixing is added, in 50 DEG C, 25min is stirred with 500r/min, mixing is obtained, takes mixing
Sodium hydroxide, the mixing of 2,3- epoxypropyltrimethylchloride chloride is added in 30:0.1:2 in mass ratio, in temperature 60 C, pressure
1h is reacted under the conditions of 3.2MPa, natural pressure release to normal pressure obtains reaction material, takes reaction material 1:8 in mass ratio that volume fraction is added and is
70% ethanol solution is mixed, and is centrifuged 7min with 3000r/min, takes centrifugation object in the dry 4h of -40 DEG C of freeze driers, i.e.,
Microcrystalline cellulose must be pre-processed.
A kind of impact resistance high-stability type material, according to the mass fraction, including following component: 2 parts of zinc stearates, 3 parts of asphalt mixtures modified by epoxy resin
Rouge, 1 part of antioxidant, 2 parts of plasticizer, 2 parts of auxiliary materials, 25 parts of compound impact resistance base-materials, 12 parts of pretreatment microcrystalline celluloses.
A kind of preparation method of impact resistance high-stability type material, includes the following steps:
(1) according to the mass fraction, take 2 parts of zinc stearates, 3 parts of epoxy resin, 1 part of antioxidant, 2 parts of plasticizer, 2 parts of auxiliary materials,
25 parts of compound impact resistance base-materials, 12 parts of pretreatment microcrystalline celluloses；
(2) prior to 40 DEG C, zinc stearate, epoxy resin, antioxidant, compound impact resistance base-material is taken to mix in batch mixer, with
500r/min magnetic agitation 35min is warming up to 90 DEG C, pretreatment microcrystalline cellulose, plasticizer, auxiliary material mixing is added, with 1000r/
Min magnetic agitation 1h, obtains mixed material, and mixed material is put into twin-screw extruder, in 170 DEG C of melting extrusions, naturally cools to
Room temperature is to get impact resistance high-stability type material.
Embodiment 2
Pretreated starch: taking the NaOH solution that sodium sulphate is added in starch 8:1:35 in mass ratio, mass fraction is 12% to mix, with
The propylene oxide mixing of starch quality 10% is added, with the HCl solution of concentration 0.01mol/L in 700r/min magnetic agitation 60min
Adjust pH to 7.2, be stored at room temperature 4h, filter, take filter cake in 80 DEG C of oven dryings to constant weight to get pretreated starch.
Reagent A: 6:1 in mass ratio takes toluene, methylene chloride mixing to get reagent A.
Reagent B: 10:1 in mass ratio takes the sulfuric acid solution that mass fraction is 15%, NH4Cl mixes to get reagent B.
Organic reagent: 8:1 takes dimethyl sulfoxide, petroleum ether mixing to get organic reagent by volume.
Auxiliary material: 1:4:0.1 in mass ratio takes polytetrafluoroethylene (PTFE), hydroxyethyl cellulose, dopamine mixing to get auxiliary material.
Antioxidant: 6:1 in mass ratio takes double stearyl alcohol pentaerythritol diphosphites, N- phenyl-β-naphthylamine mixed
It closes to get antioxidant.
Plasticizer: 8:3 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
The preparation method of compound impact resistance base-material, includes the following steps:
(1) in 32 DEG C of water-bath, 1:4 in mass ratio takes polylactic acid, reagent A mixing, with 800r/min magnetic agitation 60min, heating
To 60 DEG C, the maleic anhydride of polylactic acid quality 40%, the sodium peroxydisulfate mixing of polylactic acid quality 8% is added, with 900r/min magnetic force
65min is stirred, reaction material is obtained, takes reaction material 1:20 in mass ratio that dehydrated alcohol mixing is added, is stored at room temperature 4h, filter, take filter
After slag washs 4 times with the ethanol solution that volume fraction is 70%, 80 DEG C of oven drying 5h are moved to, dried object is obtained；
(2) 1:40 in mass ratio takes konjaku, water that 35min is mixed in reaction kettle, and the sodium metaperiodate that konjaku quality 4% is added is mixed
Stirring is closed, 4h is stored at room temperature, konjaku material must be aoxidized, according to parts by weight, take 40 parts of dried objects, 50 parts of water, the chloro- 2- hydroxyl of 15 parts of 3-
Hydroxypropyltrimonium chloride, 12 parts of oxidation konjaku material, 5 parts of hydroxyapatites, 12 parts of pretreated starch, first take the chloro- 2- hydroxypropyl of 3-
Base trimethyl ammonium chloride, water, oxidation konjaku material, pretreated starch are mixed in reaction kettle, the NaOH solution for being 12% with mass fraction
PH value is adjusted to 8.2, hydroxyapatite, dried object mixing is added, in 85 DEG C with 800r/min magnetic agitation 3h, obtains base-material, takes
Base-material is concentrated in vacuo to constant weight in 80 DEG C of rotary evaporations to get compound impact resistance base-material.
It pre-processes the preparation of microcrystalline cellulose: in 35 DEG C, taking microcrystalline cellulose 1:20 in mass ratio that reagent B mixing is added, with
550r/min magnetic agitation 3h, obtains mixed object, takes mixed object 1:15 in mass ratio that water is added to mix, move to centrifuge with 4000r/min from
Heart 15min takes supernatant to dialyse 4 days, obtains dialysate, take dialysate in 85 DEG C of rotary evaporations, be concentrated under reduced pressure into constant weight, must be concentrated
Object takes concentrate 1:8 in mass ratio that organic reagent mixing is added, and in 65 DEG C, stirs 50min with 800r/min, obtains mixing, take mixed
Expect that sodium hydroxide, the mixing of 2,3- epoxypropyltrimethylchloride chloride, 75 DEG C of Yu Wendu, pressure is added in 50:0.3:2 in mass ratio
3h is reacted under the conditions of 4.8MPa, natural pressure release to normal pressure obtains reaction material, takes reaction material 1:12 in mass ratio that volume fraction is added and is
70% ethanol solution is mixed, and is centrifuged 13min with 4000r/min, takes centrifugation object in the dry 8h of -40 DEG C of freeze driers, i.e.,
Microcrystalline cellulose must be pre-processed.
A kind of impact resistance high-stability type material, according to the mass fraction, including following component: 5 parts of zinc stearates, 7 parts of asphalt mixtures modified by epoxy resin
Rouge, 4 parts of antioxidants, 5 parts of plasticizer, 5 parts of auxiliary materials, 50 parts of compound impact resistance base-materials, 20 parts of pretreatment microcrystalline celluloses.
A kind of preparation method of impact resistance high-stability type material, includes the following steps:
(1) according to the mass fraction, take 5 parts of zinc stearates, 7 parts of epoxy resin, 4 parts of antioxidants, 5 parts of plasticizer, 5 parts of auxiliary materials,
50 parts of compound impact resistance base-materials, 20 parts of pretreatment microcrystalline celluloses；
(2) prior to 60 DEG C, zinc stearate, epoxy resin, antioxidant, compound impact resistance base-material is taken to mix in batch mixer, with
800r/min magnetic agitation 60min is warming up to 110 DEG C, pretreatment microcrystalline cellulose, plasticizer, auxiliary material mixing is added, with 1500r/
Min magnetic agitation 3h, obtains mixed material, and mixed material is put into twin-screw extruder, in 200 DEG C of melting extrusions, naturally cools to
Room temperature is to get impact resistance high-stability type material.
Embodiment 3
Pretreated starch: taking the NaOH solution that sodium sulphate is added in starch 6:1:30 in mass ratio, mass fraction is 12% to mix, with
The propylene oxide mixing of starch quality 8% is added, with the HCl solution tune of concentration 0.01mol/L in 600r/min magnetic agitation 50min
Save pH to 6.9, be stored at room temperature 3h, filter, take filter cake in 70 DEG C of oven dryings to constant weight to get pretreated starch.
Reagent A: 5:1 in mass ratio takes toluene, methylene chloride mixing to get reagent A.
Reagent B: 8:1 in mass ratio takes the sulfuric acid solution that mass fraction is 15%, NH4Cl mixes to get reagent B.
Organic reagent: 6:1 takes dimethyl sulfoxide, petroleum ether mixing to get organic reagent by volume.
Auxiliary material: 1:3:0.1 in mass ratio takes polytetrafluoroethylene (PTFE), hydroxyethyl cellulose, dopamine mixing to get auxiliary material.
Antioxidant: 5:1 in mass ratio takes double stearyl alcohol pentaerythritol diphosphites, N- phenyl-β-naphthylamine mixed
It closes to get antioxidant.
Plasticizer: 6:3 in mass ratio takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
The preparation method of compound impact resistance base-material, includes the following steps:
(1) in 30 DEG C of water-bath, 1:3 in mass ratio takes polylactic acid, reagent A mixing, with 600r/min magnetic agitation 50min, heating
To 50 DEG C, the maleic anhydride of polylactic acid quality 30%, the sodium peroxydisulfate mixing of polylactic acid quality 6% is added, with 700r/min magnetic force
55min is stirred, reaction material is obtained, takes reaction material 1:15 in mass ratio that dehydrated alcohol mixing is added, is stored at room temperature 3h, filter, take filter
After slag washs 3 times with the ethanol solution that volume fraction is 70%, 70 DEG C of oven drying 4h are moved to, dried object is obtained；
(2) 1:30 in mass ratio takes konjaku, water that 30min is mixed in reaction kettle, and the sodium metaperiodate that konjaku quality 2% is added is mixed
Stirring is closed, 3h is stored at room temperature, konjaku material must be aoxidized, according to parts by weight, take 30 parts of dried objects, 40 parts of water, the chloro- 2- hydroxyl of 13 parts of 3-
Hydroxypropyltrimonium chloride, 9 parts of oxidation konjaku material, 3 parts of hydroxyapatites, 9 parts of pretreated starch, first take the chloro- 2- hydroxypropyl of 3-
Trimethyl ammonium chloride, water, oxidation konjaku material, pretreated starch are mixed in reaction kettle, the NaOH solution tune for being 12% with mass fraction
PH value is saved to 7.8, hydroxyapatite, dried object mixing is added, in 80 DEG C with 500r/min magnetic agitation 2h, obtains base-material, takes base
Expect to be concentrated in vacuo to constant weight in 70 DEG C of rotary evaporations to get compound impact resistance base-material.
It pre-processes the preparation of microcrystalline cellulose: in 30 DEG C, taking microcrystalline cellulose 1:15 in mass ratio that reagent B mixing is added, with
450r/min magnetic agitation 2h, obtains mixed object, takes mixed object 1:12 in mass ratio that water is added to mix, move to centrifuge with 3500r/min from
Heart 12min takes supernatant to dialyse 3 days, obtains dialysate, take dialysate in 75 DEG C of rotary evaporations, be concentrated under reduced pressure into constant weight, must be concentrated
Object takes concentrate 1:6 in mass ratio that organic reagent mixing is added, and in 60 DEG C, stirs 40min with 700r/min, obtains mixing, take mixed
Expect that sodium hydroxide, the mixing of 2,3- epoxypropyltrimethylchloride chloride, 65 DEG C of Yu Wendu, pressure is added in 40:0.2:2 in mass ratio
2h is reacted under the conditions of 3.8MPa, natural pressure release to normal pressure obtains reaction material, takes reaction material 1:11 in mass ratio that volume fraction is added and is
70% ethanol solution is mixed, and is centrifuged 11min with 3500r/min, takes centrifugation object in the dry 6h of -40 DEG C of freeze driers, i.e.,
Microcrystalline cellulose must be pre-processed.
A kind of impact resistance high-stability type material, according to the mass fraction, including following component: 3 parts of zinc stearates, 4 parts of asphalt mixtures modified by epoxy resin
Rouge, 3 parts of antioxidants, 3 parts of plasticizer, 4 parts of auxiliary materials, 40 parts of compound impact resistance base-materials, 15 parts of pretreatment microcrystalline celluloses.
A kind of preparation method of impact resistance high-stability type material, includes the following steps:
(1) according to the mass fraction, take 3 parts of zinc stearates, 5 parts of epoxy resin, 3 parts of antioxidants, 4 parts of plasticizer, 4 parts of auxiliary materials,
35 parts of compound impact resistance base-materials, 15 parts of pretreatment microcrystalline celluloses；
(2) prior to 50 DEG C, zinc stearate, epoxy resin, antioxidant, compound impact resistance base-material is taken to mix in batch mixer, with
700r/min magnetic agitation 50min is warming up to 100 DEG C, pretreatment microcrystalline cellulose, plasticizer, auxiliary material mixing is added, with 1300r/
Min magnetic agitation 2h, obtains mixed material, and mixed material is put into twin-screw extruder, in 190 DEG C of melting extrusions, naturally cools to
Room temperature is to get impact resistance high-stability type material.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking compound impact resistance base-material.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking pretreatment microcrystalline cellulose.
Comparative example 3: the high impact material of Shanghai City company production.
The high impact material that above-described embodiment is obtained with comparative example is detected, it is detected according to GB/T 6344-2008
Tensile strength and elongation at break detect its adhesion strength and initial viscosity according to JGJ144-2004, according to GB 9622.7-
1988 detect its impact strength, obtain that the results are shown in Table 1.
Table 1:
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength/MPa | 63.21 | 62.11 | 62.15 | 60.07 | 57.82 | 53.72 |
| Elongation at break/% | 23.56 | 21.32 | 22.14 | 17.84 | 16.54 | 8.51 |
| Initial viscosity/MPas | 5000 | 5050 | 5030 | 5600 | 6500 | 15000 |
| Impact strength/kJ/m2 | 123 | 120 | 121 | 117 | 106 | 65 |
| Adhesion strength/MPa | 15.02 | 13.64 | 14.51 | 12.05 | 11.48 | 10.02 |
In summary, high impact material effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, it is described above only
For preferred mode of the invention, it is not intended to limit the invention, it is all within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of impact resistance high-stability type material, according to the mass fraction, including following component: 2 ~ 5 parts of zinc stearates, 3 ~ 7 parts of epoxies
Resin, 1 ~ 4 part of antioxidant, 2 ~ 5 parts of plasticizer, 2 ~ 5 parts of auxiliary materials, which is characterized in that further include: 25 ~ 50 parts of compound impact resistances
Base-material, 12 ~ 20 parts of pretreatment microcrystalline celluloses.
2. a kind of impact resistance high-stability type material according to claim 1, which is characterized in that the system of the compound impact resistance base-material
Preparation Method includes the following steps:
(1) in 26 ~ 32 DEG C, 1:2 ~ 4 take polylactic acid, reagent A to be mixed in mass ratio, are warming up to 48 ~ 60 DEG C, and polylactic acid is added
The maleic anhydride of quality 25 ~ 40%, the sodium peroxydisulfate of polylactic acid quality 4 ~ 8% are mixed, and obtain reaction material, take reaction material by quality
Dehydrated alcohol mixing is added than 1:12 ~ 20, is stored at room temperature, filters, filter residue is taken to be washed with ethanol solution, it is dry, obtain dried object；
(2) 1:20 ~ 40 take konjaku, water to be mixed in mass ratio, and the sodium metaperiodate that konjaku quality 1 ~ 4% is added is mixed, room
Temperature is stood, and must be aoxidized konjaku material, according to parts by weight, be taken 20 ~ 40 parts of dried objects, 30 ~ 50 parts of water, the chloro- 2- hydroxypropyl of 10 ~ 15 parts of 3-
Base trimethyl ammonium chloride, 7 ~ 12 parts of oxidation konjaku material, 2 ~ 5 parts of hydroxyapatites, 7 ~ 12 parts of pretreated starch, first take the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride, water, oxidation konjaku material, pretreated starch mixing, adjust pH value, hydroxyapatite, drying are added
Object mixing, stirs in 70 ~ 85 DEG C, obtains base-material, takes base-material rotary evaporation, is concentrated in vacuo to get compound impact resistance base-material.
3. a kind of impact resistance high-stability type material according to claim 2, which is characterized in that the reagent A in the step (1):
3 ~ 6:1 in mass ratio takes toluene, methylene chloride mixing to get reagent A.
4. a kind of impact resistance high-stability type material according to claim 2, which is characterized in that the pretreatment in the step (2)
Starch: it takes starch 4 ~ 8:1:25 in mass ratio ~ 35 that sodium sulphate, NaOH solution mixing is added, starch quality 6 ~ 10% is added
Propylene oxide mixing, adjusts pH, is stored at room temperature, and filters, takes filtration cakes torrefaction to get pretreated starch.
5. a kind of impact resistance high-stability type material according to claim 1, which is characterized in that the system of the pretreatment microcrystalline cellulose
It is standby: in 25 ~ 35 DEG C, to take microcrystalline cellulose 1:12 in mass ratio ~ 20 that reagent B is added and be mixed, obtain mixed object, take mixed object by quality
It takes supernatant to dialyse than 1:8 ~ 15 plus water mixing, centrifugation, obtains dialysate, take dialysate rotary evaporation, be concentrated under reduced pressure, must be concentrated
Object takes concentrate 1:4 in mass ratio ~ 8 that organic reagent mixing is added, and in 50 ~ 65 DEG C, stirring obtains mixing, takes mixing in mass ratio
Sodium hydroxide, the mixing of 2,3- epoxypropyltrimethylchloride chloride, 60 ~ 75 DEG C of Yu Wendu, pressure is added in 30 ~ 50:0.1 ~ 0.3:2
It is reacted under the conditions of 3.2 ~ 4.8MPa, pressure release obtains reaction material, takes reaction material 1:8 in mass ratio ~ 12 that ethanol solution mixing is added and stirs
It mixes, is centrifuged, take the freeze-drying of centrifugation object to get pretreatment microcrystalline cellulose.
6. a kind of impact resistance high-stability type material according to claim 5, which is characterized in that the organic reagent: by volume 4
~ 8:1 takes dimethyl sulfoxide, petroleum ether mixing to get organic reagent.
7. a kind of impact resistance high-stability type material according to claim 5, which is characterized in that the reagent B: in mass ratio 6 ~
10:1 takes sulfuric acid solution, NH4Cl mixes to get reagent B.
8. a kind of impact resistance high-stability type material according to claim 1, which is characterized in that the plasticizer: in mass ratio 5 ~
8:3 takes triethyl citrate, dioctyl phthalate mixing to get plasticizer.
9. a kind of impact resistance high-stability type material according to claim 1, which is characterized in that the antioxidant: in mass ratio 3
~ 6:1 takes double stearyl alcohol pentaerythritol diphosphites, the mixing of N- phenyl-β-naphthylamine to get antioxidant.
10. a kind of impact resistance high-stability type material according to claim 1, which is characterized in that the auxiliary material: 1:2 in mass ratio ~
4:0.1 takes polytetrafluoroethylene (PTFE), hydroxyethyl cellulose, dopamine mixing to get auxiliary material.
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| CN111909673A (en) * | 2020-08-25 | 2020-11-10 | 大庆中联信实石油科技开发有限公司 | Bio-based cleaning temporary plugging agent for fracture network volume fracturing and preparation method thereof |
| CN111909673B (en) * | 2020-08-25 | 2022-12-13 | 大庆中联信实石油科技开发有限公司 | Bio-based cleaning temporary plugging agent for fracture network volume fracturing and preparation method thereof |
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