CN104004304B - PVC material with shape memory function - Google Patents
PVC material with shape memory function Download PDFInfo
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- CN104004304B CN104004304B CN201410283123.0A CN201410283123A CN104004304B CN 104004304 B CN104004304 B CN 104004304B CN 201410283123 A CN201410283123 A CN 201410283123A CN 104004304 B CN104004304 B CN 104004304B
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Abstract
The invention discloses a PVC material with the shape memory function. The PVC material with the shape memory function comprises, by weight, 100 parts of PVC resin, 5-40 parts of plasticizers, 1-2.5 parts of stabilizers, 1.5-2.5 parts of lubricants, 5-10 parts of stuffing, 1-5 parts of impact modifier and 0.1-3 parts of thermo-reversible cross-linking agent. The PVC material has the good shape memory function and is applicable to the industrial field and the biomedical field.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of pvc material, especially, is related to one kind and has
The pvc material of shape memory function.
Background technology
Shape-memory material is a kind of important functional material.As branch therein, shape memory polymer material mesh
Before quickly grow, obtained very big concern.It has deformation quantity greatly, shape memory recovery temperature compared with traditional function material
Wide ranges, easy processing, consume energy low, the low advantage of cost, is expected to be applied to more areas in future.
Research currently, with respect to shape memory polymer material has been achieved for very big progress.Original research shows instead
Formula polyisoprene (tpi) has shape memory characteristic, and passes through double roll mill, and banbury extruder etc. is prepared for shape
The tpi material of shape memory characteristic.Subsequently people are prepared for having the crosslinked polyethylene of shape memory characteristic, polystyrene, poly- ammonia
The materials such as ester, promote the development of shape memory polymer material.Additionally, to prepare with regard to being reacted using thermally reversible
Shape-memory polymer also has some reports.Someone adopts the furans-maleic anhydride thermal reversion in diels-alder reaction system
Covalent cross-linking reacts, and is prepared for having the star polymer of shape-memory properties and having with polycaprolactone (pcl) as matrix
PLA (pla) material of shape memory characteristic.But, the research being related to the shape-memory material of pvc is but rarely reported.
It should be particularly mentioned that, in United States Patent (USP) us 7208550 b2, employ physics blending method by poly-vinegar acid second
The poly- methyl esters of alkene ester, acrylic acid, the poly- ethyl ester of acrylic acid, with row's polymethyl methacrylate etc. and polyvinylidene fluoride, PLA, poly-
Butyric ester, polyethylene glycol and polyvinyl chloride or polyvinylidene chloride carry out melting blending, prepare a kind of shape memory material
Material.
Compared with traditional chemical synthesis mode, the method employed in United States Patent (USP) us 7208550 b2 simplifies
Technique.But, the part macromolecule raw material for blending that this patent refers to contains fluorine atom and does not meet environmental protection demand.Additionally,
Whether the material that this patent also no records this blending gained has high shape-recovery capabilities.
In addition, in Chinese patent cn 1244761 c, disclosing a kind of preparation method of pvc flat tube.Specifically
When extrusion machining forms pvc tubing, pvc tubing is allowed to be heated to 120 after electron accelerator or Dynarad crosslinking
DEG C～180 DEG C, present elastomeric state in order to implement to deform, subsequently pass through 0.5 ton～50 tons (according to pipeline specifications size) rollings
Press and tape handler (folding machine) form the flat pvc pipeline of rolling (stacked), then shower cooling water be cooled fast to 75 DEG C with
Descend and present glassy state it is ensured that freezing stress will not discharge under stored condition.Installing need to be from flat tube during this kind of pipeline of laying
Head starts progressively to heat (high-frequency heating or inductive heating) backward to more than its melting temperature (150 DEG C～185 DEG C), flat
When pvc pipeline is heated, stress will be discharged, start continuously automatically to recover circular (or other shapes) directly backward from flat tube head
The pvc pipeline of tube shape.
In above-mentioned patent cn 1244761 c, having in the pvc tubing production process of shape memory of referring to needs spy
Different radiation appliance, defines permanently covalently cross-linked network in the pvc material after crosslinking, thermoplastic processing lost by material.
In Chinese patent cn 1238169 a, disclose a kind of reversible thermoplastic of Medical low-temperature with shape memory characteristic
Property fixing material, with thermoplastic polymer polyvinyl chloride, modifying agent eva resin or mbs resin and other auxiliary agents etc. according to one
Certainty ratio dispensing, kneading, plasticizing, calendering and compacting form.
Shape-memory material memory performance mentioned by above-mentioned patent cn 1238169 a be not it is obvious that and material not
Can reclaim and carry out thermoplastic reprocessing utilization.
At present it would be highly desirable to need to prepare shape-memory properties with cheap cost, simple technique excellent, and can be many
The secondary pvc material repeating processing and utilization.
Content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, it is found that: by including pvc resin
In the system of powder, add anti-impact modifier and thermal-reversible cross-linking agent it is achieved that the repetition processing and utilization of pvc material and memory
Original-shape purpose, thus complete the present invention.
It is an object of the invention to provide a kind of pvc material with shape memory function, this material is following heavy by including
The composition composition of amount proportioning:
Wherein, described anti-impact modifier is selected from one of halogenated butyl rubber, haloflex, ACM
Or multiple,
Described thermal-reversible cross-linking agent is selected from dicyclopentadiene carboxylic acid sodium salt, dicyclopentadiene carboxylic acid potassium salt, dicyclopentadiene
One or more of derivative carboxylate.
Another object of the present invention is to providing a kind of method preparing pvc sheet material using described pvc material, the method bag
Include following steps:
1) by 100 parts of pvc resin-oatmeals, 5～40 parts of plasticizer, 1～2.5 part of stabilizer, 1.5～2.5 parts of lubricants, 1.5
Mix in～2.5 parts of additives and 5～10 parts of fillers addition high-speed mixers；
2) by after described in step 1, material mixes, knead in double rod kneading machines, while mixing, add 1～
5 parts of anti-impact modifiers and 0.1～3 part of thermal-reversible cross-linking agent, wherein, the temperature of double rod kneading machines is set as 150～170 DEG C；
3) by bottom sheet after the material mixing uniformly in step 2, then hot pressing, wherein, molding temperature are carried out on moulding press
For 180～190 DEG C, clamp time is 30 minutes；
4) after the completion of being molded, cooling, the demoulding, obtain pvc sheet material.
Another object of the present invention is to providing a kind of method preparing pvc tubing using described pvc material, the method bag
Include following steps:
1) by 100 parts of pvc resin-oatmeals, 5～40 parts of plasticizer, 1～2.5 part of stabilizer, 1.5～2.5 parts of lubricants, 1.5
～2.5 parts of additives, 5～10 parts of fillers, add in high-speed mixer and mix, then by 1～5 part of anti-impact modifier
Add with 0.1～3 part of thermal-reversible cross-linking agent, continue high-speed stirred；
2) by after described in step 1, material mixes, discharging, then extruded in double screw extruder, obtained
Pvc tubing.
The pvc material that the present invention provides, has excellent shape memory characteristic, and the pvc material deformation recovery rate obtaining
More than 95%, greatly facilitate producing process.
In addition, the easy deformation of pvc tubing being prepared using the pvc material that the present invention provides, convenient transport, reduce into
This.
Additionally, the pvc material that the present invention provides can be processed again, reach the purpose recycling, to environment mankind friend
Good.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
For clear, clear and definite.
According to an aspect of the present invention, there is provided a kind of pvc material with shape memory function, this material by include with
The composition composition of lower weight proportion:
In above-mentioned pvc material, described pvc resin-oatmeal be selected from model sg-1, sg-2, in sg-3, sg-4, sg-5 one
Plant or multiple.
In above-mentioned pvc material, the species of described plasticizer is not so limited, it should be particularly mentioned that, plasticizer is selected from
One or more of following species plasticizer: phthalic acid lipid, phosphoric acid ester, aliphatic dibasic acid ester and epoxy
Class plasticizer.
Wherein, as phthalic ester plasticizer instantiation, phthalic acid two (2- ethyl hexyl) ester, neighbour are referred to
Dioctyl phthalate, di-n-octyl phthalate, BBP(Butyl Benzyl Phthalate, di-sec-octyl phthalate, adjacent benzene two
Formic acid dicyclohexyl maleate, dibutyl phthalate, diisobutyl phthalate, repefral, phthalic acid
Diethylester, diisononyl phthalate, diisooctyl phthalate.In particular it is preferred to dioctyl phthalate.
Wherein, phosphate plasticizer specifically includes tricresyl phosphate, triphenyl phosphate and diphenyl octyl phosphate.
In particular it is preferred to tricresyl phosphate.
As the instantiation of fatty group dibasic acid, refer to Plexol 201, diisooctyl adipate and Buddhist nun
Dragon acid diisobutyl ester.In particular it is preferred to Plexol 201.
As the instantiation of epoxy plasticiser, refer to epoxidized soybean oil, epoxy acetyl linolenic acid methyl esters, epoxy chaff
Butyl oleate, epoxy silkworm chrysalis butyl oleate, ethyl hexyl ester of epoxidized soybean oil and 9,10- octyl epoxy stearate.In particular it is preferred to
Epoxidized soybean oil.
In actual production, according to the different application field of pvc material, can be optionally using the species of plasticizer.
For example, in biomedical materials field, the preferably avirulent epoxy plasticiser of plasticizer, such as epoxidized soybean oil.And if
In hard pvc arts, then from conventional phthalic ester plasticizer.
According to the present invention, based on the pvc resin-oatmeal of 100 weight portions, plasticizer is 5～40 weight portions.If plasticizer contains
Amount is less than 5 parts, be difficult to play the effect of plasticising so that mixing relatively difficult it is impossible in blocks well, whereas if plasticizer
Content be higher than 40 parts so that the insufficient strength of pvc product.
In a preferred embodiment, the pvc resin-oatmeal based on 100 weight portions, plasticizer is 5～30 weight portions.
In a preferred embodiment, described stabilizer is selected from lead sulfate tribasic, lead stearate, zinc stearate, calcium zinc
One or more of compound stabilizer.
In particular it is preferred to one or more of lead sulfate tribasic, calcium-zinc composite stabilizing agent.
According to pvc materials application in different fields, optionally using stabilizer.
Based on the pvc resin-oatmeal of 100 weight portions, stabilizer is 1～2.5 weight portion.Stabiliser content is too high, can increase life
Produce cost, and product properties can be made to reduce, conversely, stabiliser content is too low, in mixing and mold process, high temperature can make
Obtain pvc to decompose, cause pvc product color to change, performance also can be affected.
In a preferred embodiment, the pvc resin-oatmeal based on 100 weight portions, stabilizer is 1.5～2.5 weight portions.
In above-mentioned pvc material, described lubricant be selected from chlorinated paraffin, stearic acid, calcium stearate, in pentaerythrite one
Plant or multiple.
Wherein, as the instantiation of chlorinated paraffin, chlorinated paraffin 42, chlorinated paraffin 52 and chlorinated paraffin 70 are referred to.
In particular it is preferred to chlorinated paraffin 70.
Based on the pvc resin-oatmeal of 100 weight portions, lubricant is 1.5～2.5 weight portions.
In a preferred embodiment, the pvc resin-oatmeal based on 100 weight portions, lubricant is 1.5～2 weight portions.
In above-mentioned pvc material, described anti-impact modifier is selected from halogenated butyl rubber, haloflex, acrylate
One or more of rubber.
Wherein, as the example of halogenated butyl rubber, chlorinated scoline and brombutyl are specifically referred to.
In a preferred embodiment, anti-impact modifier is ACM.
Based on the pvc resin-oatmeal of 100 weight portions, anti-impact modifier is 1～5 weight portion.If anti-impact modifier adds
Dosage is very few, does not have toughness reinforcing effect, also just cannot improve the mechanical properties such as pvc product strength, whereas if addition mistake
High it is contemplated that the soft segment that contains of rubber in itself, the performance of pvc product, such as bending property can be reduced.
In a preferred embodiment, the pvc resin-oatmeal based on 100 weight portions, impact modifier is 3～5 parts.
In a preferred embodiment, anti-impact modifier can be also a kind of impact modifier master batch, this master batch pass through with
Lower section method prepares:
A) by pvc resin-oatmeal and auxiliary agent batch mixing, then mixed material is added in high-speed mixer, under certain rotating speed,
It is sufficiently stirred for, wherein, preferred model sg-1, sg-2 of pvc resin-oatmeal, one or more of sg-3, sg-4, sg-5；
B) when mixed material temperature reaches 110 DEG C, mixed material is delivered in low speed mixer, at ambient temperature
Proceed stir, to be mixed to mixed material temperature be 40～50 DEG C when, discharging；
C) mixed material of discharging in step b is kneaded on double roll mill with impact modifier, wherein, anti-impact
Than for 1:1, especially, double rod kneading machine temperature are set as 160 DEG C to the weight of the pvc resin-oatmeal in modifying agent and step 1, here
At a temperature of, after mixing 10～15min, thin logical bottom sheet, then it is cut into pellet, obtain anti-impact modifier master batch.
In above-mentioned steps a, described auxiliary agent is conventional auxiliary agent, and concrete species is not so limited.Especially, auxiliary agent is
Dispersant, stabilizer, plasticizer, lubricant, one or more of filler.
Wherein, the parts by weight based on pvc resin-oatmeal are 100 parts, and the addition of dispersant is 1.0 parts, the adding of stabilizer
Dosage is 2.5 parts, and the addition of plasticizer is 5.0 parts, and the addition of lubricant is 0.5 part, and the addition of filler is 5.0
Part.
In step a, after mixed material adds high-speed mixer, high-speed mixer is under high velocity agitation so that material fills
Divide mixing, especially, mixing speed is 1000～1200r/min, and mixing time is 10min～15min.
In above-mentioned steps b, the mixing speed preferably 400～500r/min of low speed mixer.
In above-mentioned steps c, triangle bag can be beaten in mixing process repeatedly, so that making mixed material mixing uniformly.
The impact modifier master batch being obtained by above-mentioned preparation method, contains Active Chlorine due in its impact modifier, because
This can crosslink with thermal-reversible cross-linking agent conciliates crosslinked effect, then improve the deformation recovery rate of pvc material, and also make
Obtain pvc and repeat processing and utilization, further, it is also possible to effective reduces cost, beneficial to the popularization of industrialization.
In a preferred embodiment, described additive is selected from one of titanium dioxide, calcined kaolin, antioxidant 2246
Or it is multiple.
Based on the pvc resin-oatmeal of 100 weight portions, additive is 1.5～2.5 weight portions.In a preferred embodiment, base
In the pvc resin-oatmeal of 100 weight portions, additive is 2～2.5 weight portions.
In a preferred embodiment, described filler is in precipitated calcium carbonate, powdered whiting, activated Calcium carbonate
One or more.
Based on the pvc resin-oatmeal of 100 weight portions, filler is 5～10 weight portions.The addition of filler is too low, then not
Production cost can be effectively reduced, but if addition is excessive, mechanical property, the mechanical strength of end article can be affected again.
In a preferred embodiment, the pvc resin-oatmeal based on 100 weight portions, filler is 5～7.5 weight portions.
In above-mentioned pvc material, described thermal-reversible cross-linking agent is selected from dicyclopentadiene carboxylic acid sodium salt, dicyclopentadiene carboxylic acid
One or more of sylvite and dicyclopentadiene derivative carboxylate.
Especially, thermal-reversible cross-linking agent be selected from dicyclopentadiene dicarboxylic acids sodium salt, dicyclopentadiene dicarboxylic and
One or more of dicarboxylate of dicyclopentadiene derivative.
In a preferred embodiment, thermal-reversible cross-linking agent is Dimeric Cyclopentadiene Carboxylic Acid sodium salt, dicyclopentadiene diformazan
One or more of acid potassium salt.
Study through the present inventor and find, thermal-reversible cross-linking agent can react with Active Chlorine so as in crosslinked at low temperature, from
And be relatively easy to improve the deformation-recovery rate of pvc material, and solve in high temperature crosslinked so that pvc material regain plus
Work mobility, it is achieved that recycling of crosslinked pvc material, has saved the energy.
In addition, there is esterification in acceptable and as anti-impact modifier the ACM of thermal-reversible cross-linking agent,
Produce inierpeneirating network structure, thus effectively playing the effect of shape memory further.
Based on the pvc resin-oatmeal of 100 weight portions, thermal-reversible cross-linking agent 0.1～3 weight portion.
In a preferred embodiment, the pvc resin-oatmeal based on 100 weight portions, thermal-reversible cross-linking agent is 0.5～3 weight
Part, more preferably 0.5～1.5 weight portion.While reaching significant reversible crosslink effect, also significantly reduce cost.
According to a further aspect in the invention, there is provided a kind of method preparing pvc sheet material using above-mentioned pvc material, the party
Method comprises the following steps:
1) by 100 parts of pvc resin-oatmeals, 5～40 parts of plasticizer, 1～2.5 part of stabilizer, 1.5～2.5 parts of lubricants, 1.5
Mix in～2.5 parts of additives and 5～10 parts of fillers addition high-speed mixers；
2) by after described in step 1, material mixes, knead in double rod kneading machines, while mixing, add 1～
5 parts of anti-impact modifiers and 0.1～3 part of thermal-reversible cross-linking agent, wherein, the temperature of double rod kneading machines is set as 150～170 DEG C,
In particular it is preferred to 160 DEG C；
3) by bottom sheet after the material mixing uniformly in step 2, then hot pressing, wherein, molding temperature are carried out on moulding press
For 180～190 DEG C, especially, temperature is 180 DEG C, and clamp time is 30 minutes.
In the above-mentioned method preparing pvc sheet material, molding temperature and clamp time can affect the friendship of thermal-reversible cross-linking agent
Crosslinking degree conciliate by connection, and the setting of therefore molding temperature and time is very important.
Find through the substantial amounts of research of the present inventor, under conditions of different molding temperatures, the crosslinking of reflection crosslinking degree
The gel content of sample is different.Test result indicate that, with the rising of molding temperature, the gel content of Cross-linked samples is also gradually
Raise, during more than 190 DEG C, gel content can decline, this is probably that temperature is too high so that pvc decomposition is caused.Due to
Under conditions of 180 DEG C and 190 DEG C, the gel content of Cross-linked samples is close, and therefore, from the angle of saving energy consumption, molding temperature sets
It is set to 180 DEG C.
Additionally, the present inventor, through substantial amounts of research, has been surprisingly found that, under conditions of different process times, Cross-linked samples
Gel content different, therefore, clamp time is another one factor to be considered.
Find, clamp time is long through substantial amounts of experiment, solution cross-linking reaction can be made fully, and extend flowing time,
Lay the foundation for processing and utilization again, but, overlong time, can cause pvc to decompose, affect properties of product.Therefore, process time
30min is Best Times.
According to a further aspect in the invention, there is provided a kind of method preparing pvc tubing using above-mentioned pvc material, the party
Method comprises the following steps:
1) by 100 parts of pvc resin-oatmeals, 5～40 parts of plasticizer, 1～2.5 part of stabilizer, 1.5～2.5 parts of lubricants, 1.5
～2.5 parts of additives, 5～10 parts of fillers, add in high-speed mixer and mix, then by 1～5 part of anti-impact modifier
Add with 0.1～3 part of thermal-reversible cross-linking agent, continue high-speed stirred；
2) by after described in step 1, material mixes, discharging, then extruded in double screw extruder, obtained
Pvc tubing.
Above-mentioned gained pvc tubing, has excellent deformation recovery rate, and has excellent heat endurance and excellent
Mechanical property, simultaneously recyclable, low cost, bring more economic benefits.
Embodiment
Further describe the present invention below by way of instantiation.But these examples are only exemplary, not to this
The protection domain of invention constitutes any restriction.
Embodiment 1
The preparation of impact modifier master batch:
A) by pvc resin-oatmeal, dispersant calcium stearate, stabilizer lead sulfate tribasic according to weight than for 100:1.0:
2.5 batch mixings, are subsequently adding in high-speed mixer, under 1000-1200r/min, are sufficiently stirred for 10-15min,
B) when mixture temperature of charge reaches 110 DEG C, mixture material is delivered in low speed mixer in room temperature bar
Proceed under part stir, rotating speed be 400-500r/min, to be mixed to mixed material temperature be 40-50 DEG C when, discharging,
C) by the mixed material of discharging in step b and ACM according to weight than for 1:1 on double roll mill
Kneaded, double rod kneading machine temperature are set as 160 DEG C, beaten triangle bag in mixing process repeatedly, so that it is kneaded uniformly as far as possible, mix
After refining 10-15min, thin logical bottom sheet, then it is cut into pellet standby；
The preparation of pvc sheet material:
1) the pvc resin-oatmeal of 100g sg-5 type, 5g o-phthalic acid dibutyl ester, 2.5g lead sulfate tribasic are taken, 0.5g is hard
Resin acid, 1g calcium stearate, 5g activated Calcium carbonate, 2.5g titanium dioxide, mix in high-speed mixer,
2) by after described in step 1, material mixes, knead under conditions of the temperature of double rod kneading machines is 160 DEG C,
Addition 5.0g impact modifier pellet in the process, 0.5g thermal-reversible cross-linking agent Dimeric Cyclopentadiene Carboxylic Acid sodium,
3) after will be uniform for the material mixing in step 2, bottom sheet, hot pressing, wherein, molding temperature are subsequently carried out on moulding press
For 180 DEG C, clamp time is 30 minutes,
4) after the completion of being molded, cooling, the demoulding, obtain pvc sheet material.
Embodiment 2
The preparation of impact modifier master batch:
A) by pvc resin-oatmeal, dispersant calcium stearate, stabilizer lead sulfate tribasic according to weight than for 100:1.0:
2.5 batch mixings, are subsequently adding in high-speed mixer, under 1000-1200r/min, are sufficiently stirred for 10-15min,
B) when mixture temperature of charge reaches 110 DEG C, mixture material is delivered in low speed mixer in room temperature bar
Proceed under part stir, rotating speed be 400-500r/min, to be mixed to mixed material temperature be 40-50 DEG C when, discharging,
C) by the mixed material of discharging in step b and chlorinated scoline glue according to weight than for 1:1 in double roll mill
On kneaded, double rod kneading machine temperature are set as 160 DEG C, beat triangle bag repeatedly, so that it is kneaded uniformly as far as possible in mixing process,
After mixing 10-15min, thin logical bottom sheet, then it is cut into pellet standby；
The preparation of pvc sheet material:
1) the pvc resin-oatmeal of 100g sg-5 type, 7.5g o-phthalic acid dibutyl ester, 2.5g lead sulfate tribasic, 0.5g are taken
Stearic acid, 1g calcium stearate, 5g precipitated calcium carbonate, 2.5g titanium dioxide, mix in high-speed mixer,
2) by after described in step 1, material mixes, knead under conditions of the temperature of double rod kneading machines is 160 DEG C,
Addition 5.0g impact modifier master batch in the process, 1.0g thermal-reversible cross-linking agent Dimeric Cyclopentadiene Carboxylic Acid sodium,
3) after will be uniform for the material mixing in step 2, bottom sheet, hot pressing, wherein, molding temperature are subsequently carried out on moulding press
For 180 DEG C, clamp time is 30 minutes,
4) after the completion of being molded, cooling, the demoulding, obtain pvc sheet material.
Embodiment 3
The preparation of environment-friendly type pvc sheet material
1) the pvc resin-oatmeal of 100g sg-1 type, 30g epoxidized soybean oil, 2.5g calcium-zinc composite stabilizing agent are taken, 0.5g is stearic
Acid, 1g calcium stearate, 5g precipitated calcium carbonate, 1.5g calcined kaolin, mix in high-speed mixer,
2) by after described in step 1, material mixes, knead under conditions of the temperature of double rod kneading machines is 160 DEG C,
Addition 5.0g ACM in the process, 1.5g thermal-reversible cross-linking agent Dimeric Cyclopentadiene Carboxylic Acid sodium,
3) after will be uniform for the material mixing in step 2, bottom sheet, hot pressing, wherein, molding temperature are subsequently carried out on moulding press
For 180 DEG C, clamp time is 30 minutes,
4) after the completion of being molded, cooling, the demoulding, obtain pvc sheet material.
Embodiment 4
The preparation of impact modifier master batch:
A) by pvc resin-oatmeal, dispersant calcium stearate, stabilizer lead sulfate tribasic according to weight than for 100:1.0:
2.5 batch mixings, are subsequently adding in high-speed mixer, under 1000-1200r/min, are sufficiently stirred for 10-15min,
B) when mixture temperature of charge reaches 110 DEG C, mixture material is delivered in low speed mixer in room temperature bar
Proceed under part stir, rotating speed be 400-500r/min, to be mixed to mixed material temperature be 40-50 DEG C when, discharging,
C) by the mixed material of discharging in step b and ACM according to weight than for 1:1 on double roll mill
Kneaded, double rod kneading machine temperature are set as 160 DEG C, beaten triangle bag in mixing process repeatedly, so that it is kneaded uniformly as far as possible, mix
After refining 10-15min, thin logical bottom sheet, then it is cut into pellet standby；
The preparation of pvc tubing
1) the pvc resin-oatmeal of 100g sg-5 type, 5g o-phthalic acid dibutyl ester, 2.5g lead sulfate tribasic are taken, 0.5g is hard
Resin acid, 1g calcium stearate, 5g powdered whiting, 2.5g titanium dioxide, add in high-speed mixer and mix, then 5.0g is resisted
Impact modifier, 0.5g thermal-reversible cross-linking agent Dimeric Cyclopentadiene Carboxylic Acid sodium adds, and continues high-speed stirred,
2) by after described in step 1, material mixes, discharging, then extruded in double screw extruder, obtained
Pvc tubing.
Embodiment 5
The preparation of impact modifier master batch:
A) by pvc resin-oatmeal, dispersant calcium stearate, stabilizer lead sulfate tribasic according to weight than for 100:1.0:
2.5 batch mixings, are subsequently adding in high-speed mixer, under 1000-1200r/min, are sufficiently stirred for 10-15min,
B) when mixture temperature of charge reaches 110 DEG C, mixture material is delivered in low speed mixer in room temperature bar
Proceed under part stir, rotating speed be 400-500r/min, to be mixed to mixed material temperature be 40-50 DEG C when, discharging,
C) by the mixed material of discharging in step b and brombutyl according to weight than for 1:1 on double roll mill
Kneaded, double rod kneading machine temperature are set as 160 DEG C, beaten triangle bag in mixing process repeatedly, so that it is kneaded uniformly as far as possible, mix
After refining 10-15min, thin logical bottom sheet, then it is cut into pellet standby；
The preparation of pvc tubing
1) the pvc resin-oatmeal of 100g sg-5 type, 5g o-phthalic acid dibutyl ester, 2.5g lead sulfate tribasic are taken, 0.5g is hard
Resin acid, 1g calcium stearate, 5g activated Calcium carbonate, 2.5g titanium dioxide, add in high-speed mixer and mix, then 5.0g is resisted
Impact modifier, 0.5g thermal-reversible cross-linking agent Dimeric Cyclopentadiene Carboxylic Acid sodium adds, and continues high-speed stirred,
2) by after described in step 1, material mixes, discharging, then extruded in double screw extruder, obtained
Pvc tubing.
Comparative example 1
Repeat the preparation process of the pvc sheet material in embodiment 1, wherein, crosslinked without anti-impact modifier and thermal reversion
Agent, remaining condition is all constant.
Comparative example 2
Repeat the preparation process of the pvc sheet material in embodiment 1, wherein, without anti-impact modifier, remaining condition is all not
Become.
Comparative example 3
Repeat the preparation of the pvc tubing in embodiment 4, wherein without anti-impact modifier, remaining condition is all constant.
Test example
Deformation recovery rate
To embodiment 1, embodiment 2, embodiment 3 and comparative example 1, the sheet material obtained in comparative example 2, bend to u-shaped,
Then investigate respective deformation recovery situation at 85 DEG C, result is as shown in table 1:
Table 1
Pvc tubing caliber changes
To embodiment 3, pvc tubing obtained in embodiment 4 and comparative example 3, under the conditions of being 85 DEG C in water-bath,
Make pvc bending pipes deformation, subsequently take out, treat that its shape is fixed, at 85 DEG C, then investigate it recover the situation of deformation, result
As shown in table 2:
Table 2
Above in association with specific embodiment and exemplary example, the present invention is described in detail, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Multiple equivalencings, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is defined by claims.
Claims (11)
1. a kind of pvc material with shape memory function, this material is made up of the composition including following weight proportion:
Wherein, described thermal-reversible cross-linking agent is selected from dicyclopentadiene carboxylic acid sodium salt, dicyclopentadiene carboxylic acid potassium salt, dicyclopentadiene
One or more of derivative carboxylate；
Wherein, anti-impact modifier master batch is prepared by the following method and obtains:
A) by pvc resin-oatmeal and auxiliary agent batch mixing, then mixed material is added in high-speed mixer, under certain rotating speed, fully
Stirring；
B) when mixed material temperature reaches 110 DEG C, mixed material is delivered in low speed mixer, continues at ambient temperature
Be stirred, to be mixed to mixed material temperature be 40～50 DEG C when, discharging；
C) mixed material of discharging in step b is kneaded on double roll mill with anti-impact modifier, wherein, shock resistance
The weight of the pvc resin-oatmeal in modifying agent and step a than for 1:1, after the completion of mixing, thin logical bottom sheet, be then cut into pellet, obtain
Obtain anti-impact modifier master batch,
Described anti-impact modifier is selected from one or more of halogenated butyl rubber, haloflex, ACM.
2. pvc material according to claim 1, wherein, described thermal-reversible cross-linking agent is selected from dicyclopentadiene Sodium Dicarboxylic Acid
One or more of salt, dicyclopentadiene dicarboxylic, dicyclopentadiene derivative dicarboxylate, or/and described anti-impact
Hitting modifying agent is ACM.
3. pvc material according to claim 2, described thermal-reversible cross-linking agent be selected from Dimeric Cyclopentadiene Carboxylic Acid sodium or/and
Potassium dicyclopentadiene formate.
4. pvc material according to claim 1, wherein, in step a, described auxiliary agent is dispersant, stabilizer, plasticising
Agent, lubricant, one or more of filler,
Wherein, the weight portion based on pvc resin-oatmeal in step a is 100 parts, and the addition of dispersant is 1.0 parts, the adding of stabilizer
Dosage is 2.5 parts, and the addition of plasticizer is 5.0 parts, and the addition of lubricant is 0.5 part, and the addition of filler is 5.0
Part, mixing speed is 1000～1200r/min, and mixing time is 10min～15min, or/and
In stepb, the mixing speed of low speed mixer is 400～500r/min, or/and in step c, double roll mill
Temperature is set as 160 DEG C, and mixing time is 10～15min.
5. the pvc material according to any one of claims 1 to 3, wherein, described pvc resin-oatmeal be selected from model sg-1,
One or more of sg-2, sg-3, sg-4, sg-5, or/and
Described plasticizer is selected from one of dioctyl phthalate, phosphoric acid ester, fatty group dibasic acid, epoxidized soybean oil
Or multiple or/and
Described stabilizer is selected from one of lead sulfate tribasic, lead stearate, zinc stearate, calcium-zinc composite stabilizing agent or many
Kind, or/and
Described lubricant is selected from one or more of chlorinated paraffin, stearic acid, calcium stearate, pentaerythrite, or/and
Described additive is selected from one or more of titanium dioxide, calcined kaolin, antioxidant 2246, or/and
Described filler is selected from one or more of precipitated calcium carbonate, powdered whiting, activated Calcium carbonate.
6. pvc material according to claim 5, described plasticizer is selected from dioctyl phthalate or/and epoxy soybean
Oil, or/and
Described stabilizer is selected from lead sulfate tribasic or/and calcium-zinc composite stabilizing agent, or/and
Described lubricant is selected from stearic acid or/and calcium stearate.
7. pvc material according to claim 1, wherein, this material is made up of the composition including following weight proportion: is based on
The pvc resin-oatmeal of 100 weight portions, plasticizer is 5～30 parts, or/and stabilizer is 1.5～2.5 weight portions, or/and lubricant
For 1.5～2 weight portions, or/and anti-impact modifier master batch is 3～5 parts, or/and additive is 2～2.5 weight portions, or/and
Filler is 5～7.5 parts, or/and thermal-reversible cross-linking agent is 0.5～3 part.
8. pvc material according to claim 7, described thermal-reversible cross-linking agent is 0.5～1.5 part.
9. a kind of method that pvc sheet material prepared by utilization claim 1～3, pvc material any one of 5 and 6, the method bag
Include following steps:
1) by 100 parts of pvc resin-oatmeals, 5～40 parts of plasticizer, 1～2.5 part of stabilizer, 1.5～2.5 parts of lubricants, 1.5～2.5
Mix in part additive and 5～10 parts of fillers addition high-speed mixers；
2) after pvc resin-oatmeal described in step 1, plasticizer, stabilizer, lubricant, additive and filler being mixed,
Double roll mill kneads, while mixing, adds 1～5 part of anti-impact modifier master batch and 0.1～3 part of thermal reversion to hand over
Connection agent, wherein, the temperature of double roll mill is set as 150～170 DEG C；
3) by bottom sheet after the material mixing uniformly in step 2, then hot pressing is carried out on moulding press, wherein, molding temperature is 180
～190 DEG C, clamp time is 30 minutes；
4) after the completion of being molded, cooling, the demoulding, obtain pvc sheet material.
10. method according to claim 9, wherein, in step 2, the temperature of double roll mill is set as 160 DEG C, or/
In step 3, molding temperature is 180 DEG C.
The method that pvc tubing prepared by a kind of 11. utilization claims 1～3, pvc material any one of 5 and 6, the method bag
Include following steps:
1) by 100 parts of pvc resin-oatmeals, 5～40 parts of plasticizer, 1～2.5 part of stabilizer, 1.5～2.5 parts of lubricants, 1.5～2.5
Part additive, 5～10 parts of fillers, add in high-speed mixer and mix, then by 1～5 part of anti-impact modifier master batch
Add with 0.1～3 part of thermal-reversible cross-linking agent, continue high-speed stirred；
2) by pvc resin-oatmeal described in step 1, plasticizer, stabilizer, lubricant, additive, filler, anti-impact modifier
After master batch and thermal-reversible cross-linking agent mix, discharging, then extruded in double screw extruder, obtained pvc tubing.
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| CN104629221B (en) * | 2015-02-27 | 2017-02-01 | 北京创源市政建设工程有限公司 | Polyvinyl chloride (PVC) lining pipe |
| CN105820466A (en) * | 2016-04-21 | 2016-08-03 | 安徽华宇管道制造有限公司 | Preparation method of hard PVC (polyvinyl chloride) drainage pipe |
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| CN110483911A (en) * | 2019-07-29 | 2019-11-22 | 邵春明 | A kind of high-strength impact-resistant plastic pipe/tubing and preparation method thereof |
| CN110982191A (en) * | 2019-12-05 | 2020-04-10 | 浙江工业大学之江学院 | Shape memory material and preparation method thereof |
| WO2021159438A1 (en) * | 2020-02-14 | 2021-08-19 | Sika Technology Ag | Thermoreversibly crosslinked polyvinylchloride membrane |
| CN111440397A (en) * | 2020-05-25 | 2020-07-24 | 江苏格瑞林家居科技有限公司 | Preparation method of material with memory function |
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