CN104004304B - PVC material with shape memory function - Google Patents

Abstract

The invention discloses a PVC material with shape memory function, which is prepared from the following ingredients in weight ratio: 100 parts of polyvinyl chloride (PVC) resin, 5-40 parts of plasticizer, 1-2.5 parts of stabilizer, lubricating agent 1.5 to 2.5 parts of additives, 5 to 10 parts of fillers, 1 to 5 parts of impact modifiers, and 0.1 to 3 parts of thermally reversible crosslinking agents. The PVC material has excellent shape memory properties and can be widely used in industrial and biomedical fields.

Description

A PVC material with shape memory function

technical field

The invention belongs to the technical field of polymer materials, in particular to a PVC material, in particular to a PVC material with a shape memory function.

Background technique

Shape memory material is an important functional material. As a branch of it, shape memory polymer materials are developing rapidly and have received a lot of attention. Compared with traditional functional materials, it has the advantages of large deformation, wide shape memory recovery temperature range, easy processing, low energy consumption, and low cost. It is expected to be applied in more fields in the future.

At present, the research on shape memory polymer materials has made great progress. Initial studies have shown that trans-polyisoprene (TPI) has shape memory properties, and TPI materials with shape memory properties have been prepared by twin-roll mixers, internal mixer extruders, etc. Subsequently, people prepared cross-linked polyethylene, polystyrene, polyurethane and other materials with shape memory properties, which promoted the development of shape memory polymer materials. In addition, there are also some reports on the preparation of shape memory polymers by thermoreversible covalent crosslinking reactions. Someone used the furan-maleic anhydride thermal reversible covalent cross-linking reaction in the Diels-Alder reaction system to prepare a star polymer with shape memory properties based on polycaprolactone (PCL) and a star polymer with shape memory properties. Polylactic acid (PLA) material. However, the research on shape memory materials involving PVC is rarely reported.

It is particularly mentioned that in U.S. Patent No. 7,208,550 B2, polyvinyl acetate, polymethyl acrylate, polyethylene acrylate, polymethyl methacrylate, etc. in the same row are mixed with polyvinylidene by physical blending. A shape memory material is prepared by melt blending vinyl fluoride, polylactic acid, polyhydroxybutyrate, polyethylene glycol and polyvinyl chloride or polyvinylidene chloride.

Compared with traditional chemical synthesis methods, the method adopted in US Patent No. 7,208,550 B2 simplifies the process. However, some of the polymer materials used for blending mentioned in this patent contain fluorine atoms and do not meet the requirements of environmental protection. In addition, the patent does not record whether the blended material has high shape recovery ability.

In addition, in Chinese patent CN 1244761 C, a preparation method of a PVC flat pipe is disclosed. Specifically, when the extruder is processed to form PVC pipes, the PVC pipes are cross-linked by an electron accelerator or a gamma irradiation device and then heated to 120°C to 180°C, showing a high elastic state for easy deformation, and then through 0.5 tons to 50 tons (according to the size of the pipe specification) rolling machine and tape machine (folding machine) to form a roll (folded) of flat PVC pipe, and then rinse with cooling water to quickly cool to below 75°C and present a glass state, ensuring that it is stored The freezing stress will not be released in this state. When installing and laying this kind of pipe, it is necessary to gradually heat from the head of the flat pipe backward (high-frequency heating or induction heating) to a temperature above its melting point (150 ° C ~ 185 ° C). When the flat PVC pipe is heated, the stress will be released. From The head of the flat pipe starts to return to the PVC pipe in the shape of a circular (or other shape) straight pipe automatically and continuously backwards.

In the above-mentioned patent CN 1244761 C, a special radiation device is required in the production process of the PVC pipe with shape memory mentioned above, and a permanent covalent bond cross-linking network is formed in the cross-linked PVC material, and the material loses thermoplastic processability.

In Chinese patent CN 1238169 A, a medical low-temperature reversible thermoplastic fixing material with shape memory characteristics is disclosed, which is formulated with thermoplastic polymer polyvinyl chloride, modifier EVA resin or MBS resin and other auxiliary agents according to a certain proportion, Kneading, plasticizing, calendering and pressing.

The memory performance of the shape memory material mentioned in the above-mentioned patent CN 1238169 A is not obvious, and the material cannot be recycled for thermoplastic reprocessing.

At present, there is an urgent need to prepare PVC materials with excellent shape memory performance and repeated processing and utilization at low cost and simple process.

Contents of the invention

In order to solve the above problems, the present inventors have carried out intensive research and found that: by adding an impact modifier and a thermally reversible crosslinking agent to the system containing PVC resin powder, the repeated processing and utilization of PVC materials and memory The purpose of the original shape, thereby completing the present invention.

The object of the present invention is to provide a kind of PVC material with shape memory function, and this material is made up of the composition that comprises following weight ratio:

Wherein, the impact modifier is selected from one or more of halogenated butyl rubber, chlorinated polyethylene, and acrylate rubber,

The thermally reversible crosslinking agent is selected from one or more of dicyclopentadiene carboxylate sodium salt, dicyclopentadiene carboxylate potassium salt and dicyclopentadiene derivative carboxylate.

Another object of the present invention is to provide a kind of method utilizing described PVC material to prepare PVC sheet, and this method comprises the following steps:

1) Add 100 parts of PVC resin powder, 5-40 parts of plasticizer, 1-2.5 parts of stabilizer, 1.5-2.5 parts of lubricant, 1.5-2.5 parts of additive and 5-10 parts of filler into a high-speed mixer and mix well ;

2) After uniformly mixing the materials described in step 1, knead in a twin-roller mixer, and while kneading, add 1 to 5 parts of impact modifier and 0.1 to 3 parts of thermally reversible crosslinking agent, Among them, the temperature of the twin-roll mixer is set at 150-170°C;

3) After mixing the materials in step 2 evenly, the film is removed, and then hot-pressed on a molding machine, wherein the molding temperature is 180-190° C., and the molding time is 30 minutes;

4) After the molding is completed, cool down and demould to obtain a PVC sheet.

Another object of the present invention is to provide a kind of method utilizing described PVC material to prepare PVC pipe material, and this method comprises the following steps:

1) Add 100 parts of PVC resin powder, 5 to 40 parts of plasticizer, 1 to 2.5 parts of stabilizer, 1.5 to 2.5 parts of lubricant, 1.5 to 2.5 parts of additive, 5 to 10 parts of filler, and mix them in a high-speed mixer uniform, then add 1-5 parts of impact modifier and 0.1-3 parts of thermally reversible crosslinking agent, and continue stirring at high speed;

2) After uniformly mixing the materials described in step 1, the materials are discharged, and then extruded in a twin-screw extruder to obtain PVC pipes.

The PVC material provided by the invention has excellent shape memory characteristics, and the deformation recovery rate of the obtained PVC material is above 95%, which greatly facilitates the processing and production process.

In addition, the PVC pipe prepared by using the PVC material provided by the invention is easy to deform, convenient for transportation, and reduces the cost.

In addition, the PVC material provided by the invention can be processed again to achieve the purpose of recycling and is friendly to the environment and humans.

detailed description

The following describes the present invention in detail, and the features and advantages of the present invention will become more clear and definite along with these descriptions.

According to one aspect of the present invention, a kind of PVC material with shape memory function is provided, and this material is made up of the composition that comprises following weight ratio:

In the above PVC material, the PVC resin powder is selected from one or more models of SG-1, SG-2, SG-3, SG-4, and SG-5.

In the above-mentioned PVC material, the type of the plasticizer is not limited, and it is particularly mentioned that the plasticizer is selected from one or more of the following types of plasticizers: phthalates, Phosphate esters, aliphatic dibasic acid esters and epoxy plasticizers.

Among them, as specific examples of phthalate-based plasticizers, bis(2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, phthalate Butyl benzyl dicarboxylate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, phthalate Diethyl phthalate, Diisononyl phthalate, Diisodecyl phthalate. In particular, dioctyl phthalate is preferred.

Among them, the phosphate plasticizer specifically includes tricresyl phosphate, triphenyl phosphate and diphenyl-octyl phosphate. In particular, tricresyl phosphate is preferred.

As specific examples of the aliphatic dibasic acid ester, diisooctyl sebacate, diisooctyl adipate, and diisobutyl nylonate are mentioned. In particular, diisooctyl sebacate is preferred.

As specific examples of epoxy-based plasticizers, epoxidized soybean oil, epoxyacetyllinolenic acid methyl ester, epoxy butyl furfurate, epoxy silkworm chrysalis oleic acid butyl ester, epoxy soybean octyl oleate and 9 , 10-epoxy octyl stearate. In particular, epoxidized soybean oil is preferred.

In actual production, according to different application fields of PVC materials, the types of plasticizers can be selectively used. For example, in the field of biomedical materials, the plasticizer is preferably a non-toxic epoxy plasticizer, such as epoxidized soybean oil. And if it is in the field of rigid PVC products, commonly used phthalate plasticizers are used.

According to the present invention, based on 100 parts by weight of PVC resin powder, the amount of plasticizer is 5-40 parts by weight. If the plasticizer content is less than 5 parts, it is difficult to play a plasticizing role, making it difficult to mix and form a good sheet. On the contrary, if the plasticizer content is higher than 40 parts, the strength of PVC products will be reduced. not enough.

In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the amount of plasticizer is 5-30 parts by weight.

In a preferred embodiment, the stabilizer is selected from one or more of tribasic lead sulfate, lead stearate, zinc stearate, and calcium-zinc composite stabilizers.

In particular, one or more of tribasic lead sulfate and calcium-zinc composite stabilizers are preferred.

According to the application of PVC materials in different fields, stabilizers can be used selectively.

Based on 100 parts by weight of PVC resin powder, the stabilizer is 1-2.5 parts by weight. If the stabilizer content is too high, it will increase the production cost and reduce the performance of the product. On the contrary, if the stabilizer content is too low, the high temperature will cause the PVC to decompose during the mixing and molding process, causing the color of the PVC product to change and the performance to deteriorate. will be affected.

In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the stabilizer is 1.5-2.5 parts by weight.

In the above PVC material, the lubricant is selected from one or more of chlorinated paraffin, stearic acid, calcium stearate, and pentaerythritol.

Among them, as specific examples of the chlorinated paraffin, chlorinated paraffin 42, chlorinated paraffin 52, and chlorinated paraffin 70 are mentioned. In particular, chlorinated paraffin 70 is preferred.

Based on 100 parts by weight of PVC resin powder, the amount of lubricant is 1.5-2.5 parts by weight.

In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the amount of lubricant is 1.5-2 parts by weight.

In the above PVC material, the impact modifier is selected from one or more of halogenated butyl rubber, chlorinated polyethylene, and acrylate rubber.

Among them, as examples of the halogenated butyl rubber, chlorinated butyl rubber and brominated butyl rubber are specifically mentioned.

In a preferred embodiment, the impact modifier is an acrylate rubber.

Based on 100 parts by weight of PVC resin powder, the impact modifier is 1-5 parts by weight. If the amount of impact modifier added is too small, the effect of toughening will not be achieved, and the mechanical properties such as the strength of PVC products will not be improved. On the contrary, if the amount added is too high, considering the flexible segment contained in the rubber itself, it will decrease. The properties of PVC products, such as bending properties.

In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the impact modifier is 3-5 parts.

In a preferred embodiment, the impact modifier can also be a kind of impact modifier master batch, which is prepared by the following method:

a) Mix PVC resin powder and additives, then add the mixed material into a high-speed mixer, and stir fully at a certain speed. Among them, the preferred models of PVC resin powder are SG-1, SG-2, SG-3, One or more of SG-4 and SG-5;

b) When the temperature of the mixed material reaches 110°C, transport the mixed material to a low-speed mixer, continue stirring at room temperature, and discharge the mixture until the temperature of the mixed material is 40-50°C;

c) Mixing the mixed material discharged in step b and the impact modifier on a two-roll mixer, wherein the weight ratio of the impact modifier to the PVC resin powder in step 1 is 1:1, In particular, the temperature of the twin-roll kneader is set at 160°C. At this temperature, after kneading for 10 to 15 minutes, the sheet is thinly passed, and then cut into pellets to obtain the impact modifier masterbatch.

In the above step a, the auxiliary agent is a commonly used auxiliary agent, and the specific type is not limited. In particular, the auxiliary agent is one or more of a dispersant, a stabilizer, a plasticizer, a lubricant, and a filler.

Wherein, based on 100 parts by weight of PVC resin powder, the addition of dispersant is 1.0 parts, the addition of stabilizer is 2.5 parts, the addition of plasticizer is 5.0 parts, and the addition of lubricant is 0.5 parts , The amount of filler added is 5.0 parts.

In step a, after the mixed materials are added to the high-speed mixer, the high-speed mixer is stirred at a high speed to fully mix the materials, especially, the stirring speed is 1000-1200r/min, and the stirring time is 10min-15min.

In the above step b, the stirring speed of the low-speed mixer is preferably 400-500 r/min.

In the above step c, the triangular bag can be made several times during the mixing process, so that the mixed material can be mixed evenly.

The impact modifier masterbatch obtained by the above preparation method, because the impact modifier contains active chlorine, can cross-link and de-cross-link with the thermally reversible cross-linking agent, which improves the deformation of the PVC material. The recovery rate is improved, and PVC can be processed and utilized repeatedly. In addition, the cost can be effectively reduced, which is beneficial to the promotion of industrialization.

In a preferred embodiment, the additive is selected from one or more of titanium dioxide, calcined kaolin, and antioxidant 2246.

Based on 100 parts by weight of PVC resin powder, the additive is 1.5-2.5 parts by weight. In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the additive is 2-2.5 parts by weight.

In a preferred embodiment, the filler is selected from one or more of light calcium carbonate, heavy calcium carbonate, and active calcium carbonate.

Based on 100 parts by weight of PVC resin powder, the filler is 5-10 parts by weight. If the amount of filler added is too low, the production cost cannot be effectively reduced, but if the amount added is too high, the mechanical properties and mechanical strength of the final product will be affected.

In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the filler is 5-7.5 parts by weight.

In the above PVC material, the thermally reversible crosslinking agent is selected from one or more of dicyclopentadiene carboxylate sodium salt, dicyclopentadiene carboxylate potassium salt and dicyclopentadiene derivative carboxylate.

In particular, the thermally reversible crosslinking agent is selected from one or more of dicyclopentadiene dicarboxylate sodium salt, dicyclopentadiene dicarboxylate potassium salt and dicarboxylates of dicyclopentadiene derivatives.

In a preferred embodiment, the thermally reversible crosslinking agent is one or more of sodium dicyclopentadiene dicarboxylate and potassium dicyclopentadiene dicarboxylate.

The inventors found that the thermally reversible cross-linking agent can react with active chlorine to make it cross-linked at low temperature, thereby improving the deformation recovery rate of PVC material relatively easily, and de-crosslinking at high temperature, making PVC material Regain processing fluidity, realize recycling of cross-linked PVC material, and save energy.

In addition, the thermally reversible crosslinking agent can also undergo esterification reaction with the acrylate rubber as the impact modifier to form an interpenetrating network structure, thereby further effectively exerting the effect of shape memory.

Based on 100 parts by weight of PVC resin powder, the thermoreversible crosslinking agent is 0.1-3 parts by weight.

In a preferred embodiment, based on 100 parts by weight of PVC resin powder, the thermally reversible crosslinking agent is 0.5-3 parts by weight, more preferably 0.5-1.5 parts by weight. While achieving a remarkable reversible cross-linking effect, the cost is also greatly reduced.

According to another aspect of the present invention, a kind of method utilizing above-mentioned PVC material to prepare PVC sheet is provided, and this method comprises the following steps:

1) Add 100 parts of PVC resin powder, 5-40 parts of plasticizer, 1-2.5 parts of stabilizer, 1.5-2.5 parts of lubricant, 1.5-2.5 parts of additive and 5-10 parts of filler into a high-speed mixer and mix well ;

2) After uniformly mixing the materials described in step 1, knead in a twin-roller mixer, and while kneading, add 1 to 5 parts of impact modifier and 0.1 to 3 parts of thermally reversible crosslinking agent, Wherein, the temperature of the twin-roller kneader is set at 150-170°C, especially, preferably 160°C;

3) The material in step 2 is mixed evenly, and then the sheet is removed, and then hot-pressed on a molding machine, wherein the molding temperature is 180-190° C., in particular, the temperature is 180° C., and the molding time is 30 minutes.

In the above method for preparing PVC sheets, the molding temperature and molding time will affect the degree of crosslinking and decrosslinking of the thermoreversible crosslinking agent, so the setting of molding temperature and time is very important.

After a lot of research by the inventors, it was found that under the conditions of different molding temperatures, the gel content of the cross-linked samples, which reflects the degree of cross-linking, is different. The experimental results show that as the molding temperature increases, the gel content of the cross-linked sample also gradually increases. When the temperature exceeds 190°C, the gel content will decrease. This may be caused by the decomposition of PVC due to the high temperature. Since the gel content of the cross-linked samples is close at 180°C and 190°C, the molding temperature is set at 180°C from the perspective of energy saving.

In addition, after a lot of research, the inventor unexpectedly found that the gel content of the cross-linked sample is different under the condition of different processing time, therefore, the molding time is another factor to be considered.

After a lot of experiments, it is found that long molding time will make the de-crosslinking reaction sufficient, and prolong the flow time, laying the foundation for reprocessing and utilization. However, if the time is too long, it will cause PVC to decompose and affect product performance. Therefore, the processing time of 30min is the best time.

According to another aspect of the present invention, a kind of method utilizing above-mentioned PVC material to prepare PVC pipe is provided, and this method comprises the following steps:

1) Add 100 parts of PVC resin powder, 5 to 40 parts of plasticizer, 1 to 2.5 parts of stabilizer, 1.5 to 2.5 parts of lubricant, 1.5 to 2.5 parts of additive, 5 to 10 parts of filler, and mix them in a high-speed mixer uniform, then add 1-5 parts of impact modifier and 0.1-3 parts of thermally reversible crosslinking agent, and continue stirring at high speed;

2) After uniformly mixing the materials described in step 1, the materials are discharged, and then extruded in a twin-screw extruder to obtain PVC pipes.

The PVC pipe material obtained above has excellent deformation recovery rate, excellent thermal stability and excellent mechanical properties, and can be recycled and reused at low cost, bringing more economic benefits.

Example

The present invention is further described below by specific examples. However, these examples are only exemplary and do not constitute any limitation to the protection scope of the present invention.

Example 1

Preparation of impact modifier masterbatch:

a) Mix PVC resin powder, dispersant calcium stearate, and stabilizer tribasic lead sulfate at a weight ratio of 100:1.0:2.5, then add it to a high-speed mixer, and stir fully at 1000-1200r/min 10-15min,

b) When the temperature of the mixture material reaches 110°C, transfer the mixture material to a low-speed mixer and continue to stir at room temperature at a speed of 400-500r/min. When the temperature of the mixture material reaches 40-50°C, the material,

c) Mix the mixed material discharged in step b and the acrylate rubber in a weight ratio of 1:1 on a twin-roller mixer. The temperature of the twin-roller mixer is set at 160°C, and triangles are made during the mixing process. Wrap it several times, try to make it mix evenly, after mixing for 10-15 minutes, thin the slices, and then cut them into pellets for later use;

Preparation of PVC sheet:

1) Take 100g SG-5 type PVC resin powder, 5g dioctyl phthalate, 2.5g tribasic lead sulfate, 0.5g stearic acid, 1g calcium stearate, 5g active calcium carbonate, 2.5g titanium White powder, mixed evenly in a high-speed mixer,

2) After mixing the materials described in step 1 evenly, knead in a twin-roll mixer at a temperature of 160°C. During this process, add 5.0g of impact modifier pellets, 0.5g of thermally reversible Joint agent sodium dicyclopentadiene dicarboxylate,

3) After the materials in step 2 are mixed evenly, the film is removed, and then hot-pressed on a molding machine, wherein the molding temperature is 180° C., and the molding time is 30 minutes.

4) After the molding is completed, cool down and demould to obtain a PVC sheet.

Example 2

Preparation of impact modifier masterbatch:

a) Mix PVC resin powder, dispersant calcium stearate, and stabilizer tribasic lead sulfate at a weight ratio of 100:1.0:2.5, then add it to a high-speed mixer, and stir fully at 1000-1200r/min 10-15min,

b) When the temperature of the mixture material reaches 110°C, transfer the mixture material to a low-speed mixer and continue to stir at room temperature at a speed of 400-500r/min. When the temperature of the mixture material reaches 40-50°C, the material,

c) Mix the mixed material discharged in step b and the chlorobutyl rubber in a weight ratio of 1:1 on a twin-roll mixer, and set the temperature of the twin-roll mixer to 160° C. Beat the triangular bag several times, try to make it evenly kneaded, after kneading for 10-15 minutes, thin the slices, and then cut into pellets for later use;

Preparation of PVC sheet:

1) Get 100g SG-5 type PVC resin powder, 7.5g dioctyl phthalate, 2.5g tribasic lead sulfate, 0.5g stearic acid, 1g calcium stearate, 5g light calcium carbonate, 2.5 g titanium dioxide, mixed evenly in a high-speed mixer,

2) After mixing the materials described in step 1 evenly, knead in a twin-roll mixer at a temperature of 160°C. During this process, add 5.0g of impact modifier masterbatch, 1.0g of thermally Joint agent sodium dicyclopentadiene dicarboxylate,

3) After the materials in step 2 are mixed evenly, the film is removed, and then hot-pressed on a molding machine, wherein the molding temperature is 180° C., and the molding time is 30 minutes.

4) After the molding is completed, cool down and demould to obtain a PVC sheet.

Example 3

Preparation of environment-friendly PVC sheet

1) Get the PVC resin powder of 100g SG-1 type, 30g epoxy soybean oil, 2.5g calcium-zinc composite stabilizer, 0.5g stearic acid, 1g calcium stearate, 5g light calcium carbonate, 1.5g calcined kaolin, Mix well in a high-speed mixer,

2) After mixing the materials described in step 1 evenly, knead in a twin-roll mixer at a temperature of 160°C. During this process, add 5.0g of acrylate rubber, 1.5g of thermally reversible crosslinking agent dicyclopentadiene Sodium Diene Dicarboxylate,

3) After the materials in step 2 are mixed evenly, the film is removed, and then hot-pressed on a molding machine, wherein the molding temperature is 180° C., and the molding time is 30 minutes.

4) After the molding is completed, cool down and demould to obtain a PVC sheet.

Example 4

Preparation of impact modifier masterbatch:

a) Mix PVC resin powder, dispersant calcium stearate, and stabilizer tribasic lead sulfate at a weight ratio of 100:1.0:2.5, then add it to a high-speed mixer, and stir fully at 1000-1200r/min 10-15min,

b) When the temperature of the mixture material reaches 110°C, transfer the mixture material to a low-speed mixer and continue to stir at room temperature at a speed of 400-500r/min. When the temperature of the mixture material reaches 40-50°C, the material,

c) Mix the mixed material discharged in step b and the acrylate rubber in a weight ratio of 1:1 on a twin-roller mixer. The temperature of the twin-roller mixer is set at 160°C, and triangles are made during the mixing process. Wrap it several times, try to make it mix evenly, after mixing for 10-15 minutes, thin the slices, and then cut them into pellets for later use;

Preparation of PVC pipe

1) Take 100g SG-5 type PVC resin powder, 5g dioctyl phthalate, 2.5g tribasic lead sulfate, 0.5g stearic acid, 1g calcium stearate, 5g heavy calcium carbonate, 2.5g Add titanium dioxide into a high-speed mixer and mix evenly, then add 5.0g of impact modifier and 0.5g of thermally reversible crosslinking agent sodium dicyclopentadiene dicarboxylate, continue high-speed stirring,

2) After uniformly mixing the materials described in step 1, the materials are discharged, and then extruded in a twin-screw extruder to obtain PVC pipes.

Example 5

Preparation of impact modifier masterbatch:

a) Mix PVC resin powder, dispersant calcium stearate, and stabilizer tribasic lead sulfate at a weight ratio of 100:1.0:2.5, then add it to a high-speed mixer, and stir fully at 1000-1200r/min 10-15min,

b) When the temperature of the mixture material reaches 110°C, transfer the mixture material to a low-speed mixer and continue to stir at room temperature at a speed of 400-500r/min. When the temperature of the mixture material reaches 40-50°C, the material,

c) Mix the mixed material discharged in step b and bromobutyl rubber in a weight ratio of 1:1 on a twin-roller mixer. The temperature of the twin-roller mixer is set at 160°C. During the mixing process, Make triangular bags several times, try to make it evenly mixed, after mixing for 10-15 minutes, thin the slices, and then cut into pellets for later use;

Preparation of PVC pipe

1) Take 100g SG-5 type PVC resin powder, 5g dioctyl phthalate, 2.5g tribasic lead sulfate, 0.5g stearic acid, 1g calcium stearate, 5g active calcium carbonate, 2.5g titanium Add white powder to a high-speed mixer and mix evenly, then add 5.0g of impact modifier and 0.5g of thermally reversible crosslinking agent sodium dicyclopentadiene dicarboxylate, and continue stirring at high speed.

2) After uniformly mixing the materials described in step 1, the materials are discharged, and then extruded in a twin-screw extruder to obtain PVC pipes.

Comparative example 1

The preparation process of the PVC sheet in Example 1 was repeated, wherein no impact modifier and thermally reversible crosslinking agent were added, and other conditions remained unchanged.

Comparative example 2

The preparation process of the PVC sheet in Example 1 was repeated, wherein no impact modifier was added, and other conditions remained unchanged.

Comparative example 3

The preparation of the PVC pipe in Example 4 was repeated, wherein no impact modifier was added, and other conditions remained unchanged.

Test case

Deformation recovery rate

The sheets obtained in Example 1, Example 2, Example 3 and Comparative Example 1 and Comparative Example 2 were bent into a U shape, and then the respective deformation recovery conditions were investigated at 85° C. The results are shown in Table 1 :

Table 1

PVC pipe diameter change

For the PVC pipes obtained in Example 3, Example 4 and Comparative Example 3, bend and deform the PVC pipes in a water bath at 85°C, then take them out, wait for their shape to be fixed, and then examine their properties at 85°C. The results of recovery deformation are shown in Table 2:

Table 2

The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions and implementations of the present invention, all of which fall within the scope of the present invention. The protection scope of the present invention shall be determined by the appended 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.