CN115109205B - siloxane-ethylene-PS microsphere, PERT floor heating pipe and preparation method and application thereof - Google Patents
siloxane-ethylene-PS microsphere, PERT floor heating pipe and preparation method and application thereof Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C08L23/04—Homopolymers or copolymers of ethene
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/754—Self-cleaning
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- B32B2597/00—Tubular articles, e.g. hoses, pipes
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Abstract
The invention relates to a siloxane-ethylene-PS microsphere, a PERT floor heating pipe and a preparation method thereof. The preparation method of the siloxane-ethylene-PS microsphere comprises the following steps: s1, carrying out in-situ polymerization reaction on polystyrene microspheres and ethylene monomers to obtain ethylene-PS microspheres; s2, carrying out polymerization reaction on the ethylene-PS microspheres and vinyl siloxane at the temperature of 68-70 ℃ and the pH value of 6-6.5 to obtain the siloxane-ethylene-PS microspheres. The PS microsphere of the siloxane-ethylene-PS microsphere is provided with an alkyl chain segment, and the alkyl chain segment is grafted with a siloxane group, so that the siloxane-ethylene-PS microsphere has good compatibility with PERT resin, the inner wall surface of a PERT floor heating pipe forms a large contact angle with water, the surface energy is low, the inner wall surface of the PERT floor heating pipe has a self-cleaning effect, dirt deposition is avoided, and the excellent dirt-resisting effect is achieved.
Description
Technical Field
The invention relates to the field of plastic pipes, in particular to a siloxane-ethylene-PS microsphere, a PERT floor heating pipe, a preparation method and application thereof.
Background
Along with the improvement of living standard, consumers also put forward higher requirements on comfort and sanitation of home life, and especially in the field of household floor heating, the requirements on floor heating pipes are continuously improved. Many cities in north China have household heating in winter, and household heating is commonly used for PERT floor heating pipes. The existing PERT floor heating pipes mainly have the following problems: in the long-term use process of the PERT floor heating pipe, dirt is easy to generate on the inner wall, and the service life of the floor heating pipe and the indoor environmental sanitation are seriously affected. In addition, certain thickness dirt can produce negative effect to PERT ground heating coil's radiating efficiency, is difficult to guarantee indoor temperature's travelling comfort.
In the prior art, the anti-fouling performance of the inner wall of the PERT floor heating pipe is generally improved by adding a silicon-containing hydrophobic material (such as Chinese patent named as an organosilicone master batch, a self-cleaning PERT floor heating pipe and a preparation method thereof), but the compatibility of the silicon-containing hydrophobic material and PERT resin is poor, so that the anti-fouling performance of the PERT floor heating pipe is improved only to a limited extent.
Therefore, there is a need to solve the problem of poor anti-scaling effect of the PERT floor heating pipes.
Disclosure of Invention
The primary purpose of the invention is to overcome the problem of poor anti-scaling effect of the PERT floor heating pipes in the prior art, and provide a preparation method of siloxane-ethylene-PS microspheres. The PS microsphere of the siloxane-ethylene-PS microsphere is provided with an alkyl chain segment, and the alkyl chain segment is grafted with a siloxane group, so that the siloxane-ethylene-PS microsphere has good compatibility with PERT resin, the inner wall surface of a PERT floor heating pipe forms a large contact angle (138-146 degrees) with water, and the inner wall surface of the PERT floor heating pipe has a self-cleaning effect and an excellent anti-fouling effect. In addition, the PERT floor heating pipe has excellent dirt-resistant effect, so that dirt can be prevented from being generated to negatively influence the heat radiation performance of the PERT floor heating pipe, and the PERT floor heating pipe can maintain good heat radiation performance for a long time.
It is a further object of the present invention to provide a silicone-ethylene-PS microsphere.
It is a further object of the present invention to provide the use of the above-described silicone-ethylene-PS microspheres as an anti-fouling agent in the preparation of a PERT floor heating pipe.
It is yet another object of the present invention to provide a PERT floor heating tube.
It is still another object of the present invention to provide a method of manufacturing the above-mentioned PERT floor heating pipe.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a siloxane-ethylene-PS microsphere comprises the following steps:
s1, carrying out in-situ polymerization reaction on polystyrene microspheres and ethylene monomers to obtain ethylene-PS microspheres;
s2, carrying out polymerization reaction on the ethylene-PS microspheres and vinyl siloxane at the temperature of 68-70 ℃ and the pH value of 6-6.5 to obtain the siloxane-ethylene-PS microspheres.
Existing PS@SiO 2 The hydrophobic material is generally prepared by in-situ hydrolyzing tetraethoxysilane on the surface of PS microsphere (polystyrene microsphere) to form PS@SiO 2 Composite microsphere, then pass PS@SiO 2 The hydrolytic polycondensation reaction of the silicon-oxygen radical on the surface of the composite microsphere and hydrophobic agent (such as hexadecyl trimethoxy silane and heptadecafluoro decyl trimethoxy silane) to modify the hydrophobic chain segment to PS@SiO 2 And compounding the microsphere surface to obtain the raspberry-shaped particles with hydrophobicity. But PS@SiO 2 The hydrophobic material is added into the formula of the PERT floor heating pipe, and the PS@SiO 2 The hydrophobic material has poor compatibility with the PERT resin, so that the improvement of the dirt-resistant effect of the PERT floor heating pipe is limited.
The inventors of the present invention tried to replace ps@sio with alkyl segments 2 SiO of composite microsphere 2 Groups to promote compatibility of the hydrophobic material with the PERT resin, for example: the ethylene-PS microspheres are obtained by in-situ polymerization of polystyrene microspheres and ethylene monomers, but the ethylene-PS microspheres do not have a reactive group capable of being connected with a siloxane group of a siloxane substance, so that a hydrophobic segment cannot be grafted to the ethylene-PS microspheres.
The inventors of the present invention have tried to modify ethylene-PS microspheres with vinyl siloxane, but during the reaction, vinyl siloxane itself is liable to undergo hydrolytic polycondensation reaction, and it is also difficult to modify ethylene-PS microspheres.
The inventor of the present invention found through many researches that, under specific temperature and pH conditions, vinyl siloxane is selected to react with ethylene-PS microspheres, hydrophobic groups can be successfully modified on the ethylene-PS microspheres, and then the siloxane-ethylene-PS microspheres are obtained, and the reason is that: under the specific temperature and pH conditions, the hydrolysis polycondensation reaction of the vinyl siloxane can be restrained to a large extent, and meanwhile, the vinyl siloxane can be polymerized on the alkyl chain segment on the surface of the ethylene-PS microsphere through the carbon-carbon double bond to form a hydrophobic chain segment, so that the siloxane-ethylene-PS microsphere is obtained. The structure of the siloxane-ethylene-PS microsphere is as follows: based on PS microsphere, the surface of PS microsphere has alkyl chain segment, which grafts siloxane hydrophobic group, wherein the alkyl chain segment makes the siloxane-ethylene-PS microsphere have good compatibility with PERT resin, and the siloxane hydrophobic group has hydrophobicity. The siloxane-ethylene-PS microspheres are used as an anti-fouling agent to be added into an inner layer component of the PERT floor heating pipe, the alkyl chain segment enables the anti-fouling agent to have molecular-level compatibility with PERT resin, the anti-fouling agent can be uniformly dispersed in a PERT resin material, and the anti-fouling agent is matched with the hydrophobic effect of a siloxane hydrophobic group, so that the inner wall surface of the PERT floor heating pipe forms a very large contact angle (138-146 degrees) with water, the surface energy is extremely low, the inner wall surface of the PERT floor heating pipe has a self-cleaning effect, and fouling deposition is avoided, so that the anti-fouling effect is excellent. In addition, the PERT floor heating pipe has excellent dirt-resistant effect, so that dirt can be prevented from being generated to negatively influence the heat radiation performance of the PERT floor heating pipe, and the PERT floor heating pipe can maintain good heat radiation performance for a long time.
In the step S2, if the temperature is too high, the reaction rate of the vinyl siloxane self-polymerization is too fast, the polymerization degree is uncontrollable in a short period, the geometric quantity of the polymerization degree is increased, and the formed vinyl siloxane polymer is difficult to modify to ethylene-PS microspheres; if the temperature is too low, the vinyl siloxane and the ethylene-PS microsphere cannot undergo polymerization reaction, and the surface of the ethylene-PS microsphere cannot form a hydrophobic chain segment; if the pH is too low, the vinyl siloxane can generate hydrolysis polycondensation reaction, the vinyl siloxane is difficult to generate polymerization reaction on the alkyl chain segment on the surface of the ethylene-PS microsphere through carbon-carbon double bonds, and the hydrophobic chain segment cannot be modified on the ethylene-PS microsphere; if the pH is approximately equal to 7 (neutral or nearly neutral), the reactivity of the vinyl siloxane through the polymerization reaction of the carbon-carbon double bond on the alkyl chain segment on the surface of the ethylene-PS microsphere is low, and the obtained product has low silica content and poor hydrophobic effect; if the pH is too high (alkaline), the vinyl siloxane also rapidly hydrolyzes and ethylene-SiO is formed 2 Microsphere, ethylene-SiO with larger volume 2 The microsphere is difficult to be modified on ethylene-PS microsphere, and the ethylene-SiO with smaller volume 2 The microsphere can be modified to an ethylene-PS microsphere to a certain extent, but the obtained product has little silica content, uneven distribution and poor hydrophobic effect.
Preferably, the in-situ polymerization in step S1 is performed by: adding ethylene monomer, initiator and metallocene catalyst into polystyrene microsphere emulsion, and reacting at 75-90 deg.c for 25-35 min to obtain ethylene-PS microsphere.
More preferably, the initiator is at least one of ammonium persulfate, potassium persulfate, or hydrogen peroxide.
More preferably, the metallocene catalyst is at least one of titanocene dichloride, methylaluminoxane or trimethylaluminum.
More preferably, the reaction is carried out under stirring at a speed of 400 to 550rpm.
More preferably, the polystyrene microsphere emulsion is prepared by the following steps: adding a styrene monomer and an initiator into a solvent containing an emulsifier, and carrying out polymerization reaction in an inert gas atmosphere to obtain the polystyrene microsphere emulsion.
Further preferably, the initiator is at least one of ammonium persulfate, potassium persulfate, or hydrogen peroxide.
Further preferably, the emulsifier is at least one of polyvinyl alcohol, polyethylene glycol or polyoxyethylene ether.
Further preferably, the solvent is at least one of water, ethanol or diethyl ether.
Further preferably, the inert gas is at least one of nitrogen, helium or neon.
Further preferably, the reaction temperature of the polymerization reaction is 75-90 ℃ and the reaction time is 25-35 min.
Further preferably, the polymerization is carried out under stirring at a speed of 350 to 500rpm.
Preferably, the reaction time of the reaction in step S2 is 120 to 180 minutes.
Preferably, the mass ratio of the polystyrene microsphere in the step S1 to the ethylene monomer in the step S1 is 1 (0.3-0.5); the mass ratio of the polystyrene microsphere in the step S1 to the vinyl siloxane in the step S2 is 1 (0.05-0.1).
Preferably, the vinyl siloxane in step S2 is at least one of vinyl trimethoxy silane, vinyl triethoxy silane or vinyl methyl dimethoxy silane.
Preferably, an initiator is further added in the polymerization reaction in the step S2, and the initiator is at least one of ammonium persulfate, potassium persulfate or hydrogen peroxide.
Preferably, a surfactant is further added in the polymerization reaction in the step S2, and the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate or sodium dodecyl sulfate.
Preferably, the reaction in step S2 is carried out under stirring at a speed of 120 to 200rpm.
Preferably, the reaction in step S2 is completed further comprising the steps of purification, separation and drying.
The siloxane-ethylene-PS microsphere is prepared by the preparation method.
The application of the siloxane-ethylene-PS microspheres as an anti-fouling agent in preparing PERT floor heating pipes.
A PERT floor heating pipe, comprising an inner layer and an outer layer;
the inner layer comprises the following components in parts by weight:
100 parts of PERT resin,
7-10 parts of the siloxane-ethylene-PS microsphere,
2-5 parts of color masterbatch.
The siloxane-ethylene-PS microspheres are added into the inner layer of the PERT floor heating pipe, so that the inner wall surface of the PERT floor heating pipe forms a large contact angle (138-145 degrees) with water, the surface energy is reduced, the inner wall surface of the PERT floor heating pipe has a self-cleaning effect, dirt deposition is avoided, and the anti-dirt effect is excellent. In addition, the PERT floor heating pipe has excellent dirt-resistant effect, so that dirt can be prevented from being generated to cause negative influence on the heat radiation performance of the PERT floor heating pipe, and the PERT floor heating pipe keeps good heat radiation performance for a long time.
Preferably, the PERT resin is at least one of hexene copolymerized heat resistant polyethylene or butene copolymerized heat resistant polyethylene.
Preferably, the color master is at least one of a white master, a red master, or a purple master.
The PERT floor heating pipe generally comprises an inner layer and an outer layer, and the thickness ratio of the inner layer and the outer layer which are conventional in the art are suitable for the invention.
Preferably, the thickness ratio of the inner layer to the outer layer is 1: (8-10).
The outer layer formulation of the PERT floor heating pipe conventional in the art can be used in the present invention.
Preferably, the outer layer comprises the following components in parts by weight:
more preferably, the PERT resin is at least one of hexene copolymerized heat resistant polyethylene or butene copolymerized heat resistant polyethylene;
more preferably, the heat conductive filler is modified graphene, and the modified graphene is aliphatic acid modified graphene with 12-20 carbon atoms.
The graphene is modified by adopting the aliphatic acid with the carbon number of 12-20, so that the aggregation of the graphene in the PERT resin can be avoided, the heat dissipation performance of the PERT floor heating pipe can be further improved, and the ash content of the PERT floor heating pipe can be reduced and the color dispersion problem of the PERT floor heating pipe can be improved, so that the ash content index and the color dispersion index of the PERT floor heating pipe meet the requirements of the standard GBT 28799.2-2020.
Further preferably, the modified graphene is prepared by the following steps: adding graphene powder and the aliphatic acid into a solvent, adding a surfactant and a dispersing agent, reacting under the condition that the pH is 7.3-7.5, and filtering, drying, grinding and sieving to obtain the modified graphene.
More preferably, the color master is at least one of a black master, a red master, or a purple master.
More preferably, the brightening agent is at least one of polyethylene wax, normal paraffin wax or high melting point wax.
The preparation method of the PERT floor heating pipe comprises the following steps: and respectively and uniformly mixing the components of the inner layer and the components of the outer layer, and obtaining the composite material after material drying, co-extrusion and molding.
Preferably, the mixing process is as follows: the components of the inner layer and the components of the outer layer are respectively added into two containers and stirred for 5 to 10 minutes.
Preferably, the material drying process comprises the following steps: and respectively drying the uniformly mixed inner layer components and outer layer components at 75-85 ℃ for 1.5-2 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The surface of the PS microsphere of the siloxane-ethylene-PS microsphere prepared by the preparation method provided by the invention is provided with an alkyl chain segment, and the alkyl chain segment is grafted with a siloxane group, wherein the alkyl chain segment enables the siloxane-ethylene-PS microsphere to have good compatibility with PERT resin, and the siloxane group has hydrophobicity. The siloxane-ethylene-PS microspheres are used as an anti-fouling agent to be added into an inner layer component of the PERT floor heating pipe, the anti-fouling agent and PERT resin are compatible in molecular level through the alkyl chain segment, the anti-fouling agent can be uniformly dispersed in the PERT resin material, and the inner wall surface of the PERT floor heating pipe forms a large contact angle (135-145) with water through the hydrophobic effect of the hydrophobic chain segment, so that the surface energy is reduced, the inner wall surface of the PERT floor heating pipe has a self-cleaning effect, fouling deposition is avoided, and the excellent anti-fouling effect is achieved. In addition, the PERT floor heating pipe has excellent dirt-resistant effect, so that dirt can be prevented from being generated to negatively influence the heat radiation performance of the PERT floor heating pipe, and the PERT floor heating pipe can maintain good heat radiation performance for a long time.
(2) The siloxane-ethylene-PS microspheres are added into the inner layer of the PERT floor heating pipe, so that the inner wall surface of the PERT floor heating pipe forms a large contact angle (135-146 degrees) with water, the inner wall surface of the PERT floor heating pipe has a self-cleaning effect and avoids dirt deposition, and the PERT floor heating pipe has an excellent dirt-resisting effect. In addition, the PERT floor heating pipe has excellent dirt-resistant effect, so that dirt can be prevented from being generated to cause negative influence on the heat radiation performance of the PERT floor heating pipe, and the PERT floor heating pipe keeps good heat radiation performance for a long time.
Drawings
Fig. 1 is a schematic structural view of a cross section of a PERT floor heating pipe of embodiment 1.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
The reagents selected for the examples and comparative examples of the present invention are described below:
PERT resin: dayer, XRT70, hexene copolymerized heat resistant polyethylene;
color master batch: australia color, SZ19049, white master;
and (3) brightening agent: australian, Z0435, polyethylene wax;
antifoulant # 1 (silicone-ethylene-PS microsphere # 1): the self-making method comprises the following steps:
1) 50 parts of emulsifier polyvinyl alcohol (Maillard, suzhou) and 100 parts of distilled water are added into a reaction kettle, stirring is started, the speed is 200rpm, and the temperature is heated to 70 ℃ by water bath, so that the polyvinyl alcohol is completely dissolved.
2) 0.3 part of initiator and 10 parts of styrene monomer are weighed and added into a reaction kettle, and the mixture is stirred and reacted for 30min at 85 ℃ under nitrogen atmosphere, wherein the stirring speed is 400rpm, so that PS microsphere emulsion is obtained.
3) Dissolving 3 parts of ethylene monomer in an ethanol solvent, adding the ethanol solvent into PS microsphere emulsion, adding 0.15 part of potassium persulfate and 3 parts of metallocene catalyst (dichloro-titanocene, TH-58, zibo-new plastic) at the same time, stirring and reacting for 30min at the temperature of 85 ℃, wherein the stirring speed is 500rpm, and blue light appears in a reaction system to obtain ethylene-PS microsphere emulsion;
4) The temperature of the ethylene-PS microsphere emulsion is regulated to 68 ℃, 1 part of vinyl siloxane, 0.5 part of ammonium persulfate, 0.4 part of sodium dodecyl benzene sulfonate and 3 parts of acetic acid solution (the concentration is 0.05 mol/L) are added, and the mixture is stirred and reacted for 2.5 hours under the conditions of pH=6.2 and 69 ℃ at the stirring speed of 180rpm; then cooling the reaction system to 50 ℃, condensing and refluxing for 3 hours, filtering to obtain emulsion, and drying the emulsion at 90 ℃ to obtain the siloxane-ethylene-PS microsphere No. 1.
Antifoulant # 2 (silicone-ethylene-PS microsphere # 2): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in the step 4) was carried out at a temperature of 68℃in the reaction system.
Antifoulant 3# (siloxane-ethylene-PS microsphere 3 #): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in the step 4) is carried out under the condition that the temperature of the reaction system is 70 ℃.
Antifoulant # 4 (silicone-ethylene-PS microsphere # 4): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in step 4) was carried out under the condition that ph=6.0 of the reaction system.
Antifoulant # 5 (silicone-ethylene-PS microsphere # 5): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in step 4) was carried out at a ph=6.5 of the reaction system.
Antifoulant # 6 (silicone-ethylene-PS microsphere # 6): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in the step 4) was carried out at a temperature of 75℃in the reaction system to give a white mass, and the siloxane-ethylene-PS microspheres could not be obtained.
Antifoulant # 7 (silicone-ethylene-PS microsphere # 7): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in the step 4) is performed under the condition that the ph=5.5 of the reaction system, the vinyl siloxane can generate hydrolysis polycondensation reaction by itself, the vinyl siloxane is difficult to polymerize on the ethylene-PS microsphere, and the silicone-ethylene-PS microsphere cannot be obtained.
Antifoulant # 8 (silicone-ethylene-PS microsphere # 8): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in the step 4) is carried out under the condition that the pH=7 of the reaction system, so as to obtain the siloxane-ethylene-PS microsphere 8#. The reactivity of the polymerization reaction under neutral conditions is low, and the silicon content on the silicon-ethylene-PS microsphere is low.
Antifoulant # 9 (silicone-ethylene-PS microsphere # 9): the self-made preparation method is different from the preparation method of the anti-fouling agent 1# in that: the stirring reaction in the step 4) is carried out under the condition that the pH=8 of the reaction system, so as to obtain the siloxane-ethylene-PS microsphere 9#. Under the condition of too strong alkalinity, vinyl siloxane itself is hydrolyzed faster and competes with the polymerization formation of carbon-carbon double bonds, resulting in a low silicon content on the siloxane-ethylene-PS microspheres.
Heat conductive filler # 1: new australia, unmodified graphene;
heat conductive filler # 2: modified graphene: the self-making method comprises the following steps:
1) Adding 100 parts of unmodified graphene (heat-conducting filler 1#) into a surface activation reaction kettle, wherein the stirring speed of a stirrer is 500rpm/min; dissolving stearic acid in a mixed solution of absolute ethyl alcohol and chloroform to obtain a stearic acid saturated organic solution;
2) Adding 1.5 parts of stearic acid saturated organic solution and 2 parts of sodium dodecyl benzene sulfonate into a surface activation reaction kettle, and stirring for 10min;
3) Then adding 0.5 part of polyacrylamide potassium salt and 0.3 part of sodium bicarbonate solution (the concentration is 0.2 mol/L) into a surface activation reaction kettle, regulating the pH value of the solution to 7.4, stirring for 10min, standing for 5h, vacuum filtering, drying at the constant temperature of 80 ℃ for 4h to obtain a solid substance, grinding the solid substance by a pulverizer, and sieving the solid substance by a 300-mesh sieve to obtain the modified graphene.
Examples 1 to 9
Examples 1-9 provide a series of PERT floor heating pipes comprising an inner layer and an outer layer, the inner layer having a thickness of 0.15mm and the outer layer having a thickness of 1.35mm. The formulations of the inner and outer layers are shown in table 1. The preparation process of the PERT floor heating pipes of each embodiment is as follows: respectively adding the components of the inner layer and the components of the outer layer into different charging barrels, respectively stirring for 5 minutes, and respectively uniformly mixing; respectively drying the uniformly mixed inner layer components and outer layer components at 80 ℃ for 2 hours; and adopting a co-extruder to realize composite co-extrusion of the components of the inner layer and the outer layer in a co-extruder head in a molten state, and finally realizing shaping, cooling, traction and cutting of the pipe through forming auxiliary equipment to obtain a PERT floor heating pipe finished product. A schematic of the cross-sectional structure of the PERT floor heating pipe of example 1 is shown in fig. 1.
Table 1 composition formulation and thickness of inner and outer layers of PERT floor heating pipes of examples
Comparative example 1
This comparative example provides a PERT floor heating pipe which differs from example 1 in that: the inner layer component of the anti-fouling agent 1# was replaced with the anti-fouling agent 8#.
Comparative example 2
This comparative example provides a PERT floor heating pipe which differs from example 1 in that: the inner layer component of the anti-fouling agent 1# was replaced with the anti-fouling agent 9#.
Comparative example 3
This comparative example provides a PERT floor heating pipe which differs from example 1 in that: no anti-fouling agent # 1 is added to the inner layer component.
Performance testing
The following performance tests were performed on the PERT floor heating pipes obtained in each example and comparative example:
thermal conductivity coefficient: test standard GBT 10297-2015;
contact angle (unfoamed water): test standard GBT 30693-2014;
contact angle (6 months use): test standard GBT 30693-2014;
ash content: test standard GBT 28799.2-2020, standard requirements: less than or equal to 0.8 percent;
and (3) pigment dispersion: test standard GBT 28799.2-2020, standard requirements: the size grade is less than or equal to 3, and the apparent grade is A1, A2, A3 or B.
The test results of each example and comparative example are shown in table 2.
Table 2 results of performance testing of the PERT floor heating pipes of each of the examples and comparative examples
As is clear from Table 2, the contact angle of the unfoamed water and the contact angle after 6 months of use of the PERT floor heating pipes of examples 1 to 9 were high, indicating that the addition of the siloxane-ethylene-PS microspheres of the present invention as an anti-fouling agent to the inner layer component of the PERT floor heating pipe provided good anti-fouling effect for the PERT floor heating pipes. The conditions of the preparation methods of the siloxane-ethylene-PS microspheres of comparative examples 1 and 2 are not suitable, the obtained siloxane-ethylene-PS microspheres are added as an anti-fouling agent to the inner layer component of the PERT floor heating pipe, the contact angle of the prepared PERT floor heating pipe is not obviously improved compared with the PERT floor heating pipe of comparative example 3 (no anti-fouling agent is added), and the anti-fouling effect of the PERT floor heating pipes of comparative examples 1 and 2 is not good.
Unmodified graphene was added to the outer layer component of the PERT floor heating pipe of example 8, resulting in an ash and pigment dispersion that did not meet the requirements of standard GBT 28799.2-2020.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. The preparation method of the siloxane-ethylene-PS microsphere is characterized by comprising the following steps of:
s1, carrying out in-situ polymerization reaction on polystyrene microspheres and ethylene monomers to obtain ethylene-PS microspheres;
and S2, carrying out polymerization reaction on the ethylene-PS microspheres and vinyl siloxane at the temperature of 68-70 ℃ and the pH value of 6-6.5 to obtain the siloxane-ethylene-PS microspheres.
2. The method according to claim 1, wherein the in-situ polymerization in step S1 is performed by: and adding an ethylene monomer, an initiator and a metallocene catalyst into the polystyrene microsphere emulsion, and reacting at 75-90 ℃ for 25-35 min to obtain the ethylene-PS microsphere.
3. The preparation method according to claim 1, wherein the reaction time of the reaction in the step S2 is 120-180 min.
4. The preparation method of claim 1, wherein the mass ratio of the polystyrene microsphere in the step S1 to the ethylene monomer in the step S1 is 1 (0.3-0.5); the mass ratio of the polystyrene microsphere in the step S1 to the vinyl siloxane in the step S2 is 1 (0.05-0.1).
5. The method according to claim 1, wherein the vinyl siloxane in step S2 is at least one of vinyl trimethoxysilane, vinyl triethoxysilane, or vinyl methyldimethoxysilane.
6. A siloxane-ethylene-PS microsphere prepared by the method of any one of claims 1 to 5.
7. Use of the siloxane-ethylene-PS microspheres of claim 6 as an anti-fouling agent in the preparation of a PERT floor heating pipe.
8. A PERT floor heating pipe is characterized by comprising an inner layer and an outer layer;
the inner layer comprises the following components in parts by weight:
100 parts of PERT resin,
7-10 parts of the siloxane-ethylene-PS microsphere according to claim 6,
2-5 parts of color masterbatch;
the outer layer comprises the following components in parts by weight:
100 parts of PERT resin,
0.3-0.8 part of heat conducting filler,
1-3 parts of color masterbatch,
1.5-3 parts of brightening agent;
the heat conducting filler is modified graphene, and the modified graphene is aliphatic acid modified graphene with the carbon number of 12-20.
9. The PERT floor heating of claim 8, wherein the PERT resin is at least one of hexene copolymerized heat resistant polyethylene or butene copolymerized heat resistant polyethylene; the color master is at least one of white master, red master or purple master.
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