CN109320888A - A kind of polymethyl methacrylate heat-conductive composite material and preparation method thereof - Google Patents
A kind of polymethyl methacrylate heat-conductive composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of polymer material processing more particularly to a kind of polymethyl methacrylate heat-conductive composite material and preparation method thereof.Polymethyl methacrylate heat-conductive composite material provided by the invention is by including that the raw material melt blending of following parts by weight of component is made: 100 parts of polymethyl methacrylate；2.5~15 parts of Poly L-lactic acid；2.5~15 parts of poly- L-lactic acid；0.5~30 part of heat filling；The heat filling includes at least three kinds in two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramic powder, silver powder, silicon powder, alusil alloy powder and porous crystalline flake graphite；The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than the fusing point of Stereocomplex type polylactic acid.The experimental results showed that heat-conductive composite material provided by the invention has excellent heating conduction, thermal coefficient reaches as high as 4.1W/mK or more.
Description
Technical field
The invention belongs to technical field of polymer material processing more particularly to a kind of polymethyl methacrylate are thermally conductive compound
Material and preparation method thereof.
Background technique
Polymethyl methacrylate abridges code name as PMMA, is commonly called as organic glass, is to synthesize in transparent material so far
Quality is most excellent, and price is again than convenient kind.Its density is small, good toughness, is widely used in aviation, building, agricultural, light
Learn the fields such as instrument.But some disadvantages of PMMA itself, such as wearability are poor, low using temperature, easy to produce static electricity existing
As, poor thermal conductivity etc., its application range is also limited.For these disadvantages, many study on the modification have been carried out both at home and abroad, such as
Improve its heating conduction.
Currently, it is to add heat filling in PMMA that PMMA, which leads thermally-denatured major way, but since heat filling exists
Easily reunite in PMMA, so as to cause it, dispersibility is poor in PMMA, closely causes the thermally conductive modification of the PMMA prepared
The heating conduction of material is unsatisfactory.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of polymethyl methacrylate heat-conductive composite material and its preparations
Method, composite material provided by the invention have excellent heating conduction.
The present invention provides a kind of polymethyl methacrylate heat-conductive composite materials, by the original including following parts by weight of component
Material melt blending is made:
The heat filling include two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramic powder,
At least three kinds in silver powder, silicon powder, alusil alloy powder and porous crystalline flake graphite；
The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than the poly- cream of Stereocomplex type
The fusing point of acid.
Preferably, the partial size of the heat filling is 50~2000nm.
Preferably, the heat filling include two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine,
Three kinds in ceramic powder, silver powder, silicon powder and porous crystalline flake graphite or four kinds.
Preferably, the weight average molecular weight of the polymethyl methacrylate is 5~200,000.
Preferably, the weight average molecular weight of the Poly L-lactic acid is 1~200,000.
Preferably, the weight average molecular weight of the poly- L-lactic acid is 1~200,000.
Preferably, the mass ratio of the Poly L-lactic acid and poly- L-lactic acid is 1:(0.5~2).
The present invention provides a kind of preparation sides of polymethyl methacrylate heat-conductive composite material described in above-mentioned technical proposal
Method, comprising the following steps:
A) by polymethyl methacrylate, Poly L-lactic acid, poly- L-lactic acid and heat filling melt blending, poly- first is obtained
Base methyl acrylate heat-conductive composite material；
The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than the poly- cream of Stereocomplex type
The fusing point of acid.
Preferably, in step a), the detailed process of the melt blending includes:
A1) by polymethyl methacrylate, Poly L-lactic acid and heat filling melt blending, melt is obtained；
A2) by the melt and poly- L-lactic acid melt blending, polymethyl methacrylate heat-conductive composite material is obtained.
Preferably, step a1) described in melt blending temperature be 150~180 DEG C, the time be 5~15min；
Step a2) described in melt blending temperature be 150~180 DEG C, the time be 5~15min.
Compared with prior art, the present invention provides a kind of polymethyl methacrylate heat-conductive composite material and its preparation sides
Method.Polymethyl methacrylate heat-conductive composite material provided by the invention is by the raw material melt blending including following parts by weight of component
It is made: 100 parts of polymethyl methacrylate；2.5~15 parts of Poly L-lactic acid；2.5~15 parts of poly- L-lactic acid；Heat filling
0.5~30 part；The heat filling includes two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramics
At least three kinds in powder, silver powder, silicon powder, alusil alloy powder and porous crystalline flake graphite；The temperature of the melt blending is higher than a poly- left side
The fusing point for revolving lactic acid and poly- L-lactic acid, lower than the fusing point of Stereocomplex type polylactic acid.Scheme provided by the invention uses low temperature
Melt-processed prepares composite material of polymethyl methacrylate, in such processing temperature section, Poly L-lactic acid and poly- dextrorotation
Lactic acid can melt completely, and only Stereocomplex type polylactic acid crystal can be grown, due to polylactic acid and polymethylacrylic acid
Methyl esters has good compatibility, and Stereocomplex type polylactic acid crystal, will be dispersed in the form of solid phase once being formed
In polylactic resin, the Stereocomplex type polylactic acid crystal being formed in situ greatly improves the shearing force of melt, so that thermally conductive
Filler can be dispersed in matrix, to form effective passage of heat, be further formed effective heat conduction network, Jin Ergai
The heating conduction of kind composite material.Meanwhile the present invention optimizes screening by the specific type to added heat filling, into
One step improves the heating conduction of composite material.The experimental results showed that the thermally conductive system of heat-conductive composite material provided by the invention
Number reaches as high as 4.1W/mK or more (GB/T 3399-1982).
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of polymethyl methacrylate heat-conductive composite materials, by the original including following parts by weight of component
Material melt blending is made:
The heat filling include two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramic powder,
At least three kinds in silver powder, silicon powder, alusil alloy powder and porous crystalline flake graphite；
The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than the poly- cream of Stereocomplex type
The fusing point of acid.
Polymethyl methacrylate heat-conductive composite material provided by the invention is made of raw material melt blending, wherein described
Raw material includes polymethyl methacrylate, Poly L-lactic acid, poly- L-lactic acid and heat filling.In the present invention, the poly- first
The weight average molecular weight of base methyl acrylate is preferably 5~200,000, concretely 50,000,60,000,70,000,80,000,90,000,100,000,110,000,
120000,130,000,140,000,150,000,160,000,170,000,180,000,190,000 or 200,000.
In the present invention, the weight average molecular weight of the Poly L-lactic acid is preferably 1~200,000, and concretely 10,000,20,000,3
Ten thousand, 40,000,50,000,60,000,70,000,80,000,90,000,100,000,110,000,120,000,130,000,140,000,150,000,160,000,170,000,180,000,190,000
Or 200,000.In the present invention, described to gather left-handed cream in terms of being 100 parts by weight by polymethyl methacrylate content in the feed
Acid content in the feed is 2.5~15 parts by weight, concretely 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight,
4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 weights
Measure part, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5
Parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, 14.5 parts by weight or 15 parts by weight.
In the present invention, the weight average molecular weight of the poly- L-lactic acid is preferably 1~200,000, and concretely 10,000,20,000,3
Ten thousand, 40,000,50,000,60,000,70,000,80,000,90,000,100,000,110,000,120,000,130,000,140,000,150,000,160,000,170,000,180,000,190,000
Or 200,000.It in the present invention, is the poly- dextrorotation cream in terms of 100 parts by weight by the content of polymethyl methacrylate in the feed
Acid content in the feed is 2.5~15 parts by weight, concretely 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight,
4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 weights
Measure part, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5
Parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, 14.5 parts by weight or 15 parts by weight.In a reality provided by the invention
Apply in example, mass ratio is preferably 1:(0.5~2 in the feed for the Poly L-lactic acid and poly- L-lactic acid), more preferably 1:1.
In the present invention, the heat filling includes two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadium
At least three kinds in soil, ceramic powder, silver powder, silicon powder, alusil alloy powder and porous crystalline flake graphite, preferably include three kinds or four kinds.
In the present invention, the partial size of the heat filling is preferably 50~2000nm, concretely 50nm, 80nm, 100nm, 120nm,
150nm、180nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm、1100nm、
1200nm, 1300nm, 1400nm, 1500nm, 1600nm, 1700nm, 1800nm, 1900nm or 2000nm.It is provided in the present invention
One embodiment in, the ceramic powder be ultrafine ceramic powder, the partial size of the ultrafine ceramic powder is preferably 1000~1800nm,
Concretely 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, 1500nm, 1600nm, 1700nm or 1800nm.At this
It invents in the one embodiment provided, the silicon powder is silicon powder, and the partial size of the silicon powder is preferably 500~1200nm, tool
Body can be 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm or 1200nm.At one provided by the invention
In embodiment, the heat filling include two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramic powder,
Three kinds in silver powder, silicon powder and porous crystalline flake graphite or four kinds.In one embodiment provided by the invention, the heat filling
Including aluminium nitride, two-dimentional boron nitride nanosheet and aluminium oxide, the quality of the aluminium nitride, two-dimentional boron nitride nanosheet and aluminium oxide
Than being preferably 2:(0.5~5): (2~10), more preferably 2:(1~3): (3~7), most preferably 2:2:5.It is provided in the present invention
Another embodiment in, the heat filling includes aluminium nitride, aluminium vanadine and silicon carbide, the aluminium nitride, aluminium vanadine and carbon
The mass ratio of SiClx is preferably 5:(2~10): (0.5~5), more preferably 5:(3~7): (1~3), most preferably 5:5:2.?
In other embodiments provided by the invention, the heat filling includes silver powder, silicon powder and ceramic powder, the silver powder, silicon powder and pottery
The mass ratio of porcelain powder is preferably 2.5:(0.5~5): (0.5~5), more preferably 2.5:(2~4): (2~4), most preferably
2.5:2.5:2.5.In other embodiments provided by the invention, the heat filling includes two-dimentional boron nitride nanosheet, porous
Crystalline flake graphite and silicon powder, the two dimension boron nitride nanosheet, porous crystalline flake graphite and silicon powder mass ratio be preferably 5:(2~
10): (2~10), more preferably 5:(3~7): (3~7), most preferably 5:5:5.In other embodiments provided by the invention,
The heat filling includes two-dimentional boron nitride nanosheet, aluminium nitride, silver powder and silicon carbide, the two dimension boron nitride nanosheet, nitrogen
The mass ratio for changing aluminium, silver powder and silicon carbide is 7.5:(2~12): (2~12): (2~12), more preferably 7.5:(5~10): (5
~10): (5~10), most preferably 7.5:7.5:7.5:7.5.
It in the present invention, is the heat filling in terms of 100 parts by weight by the content of polymethyl methacrylate in the feed
Content in the feed is 0.5~30 parts by weight, concretely 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5
Parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 weight
Part, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight,
11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, 14.5 weight
Part, 15 parts by weight, 15.5 parts by weight, 16 parts by weight, 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5
Parts by weight, 19 parts by weight, 19.5 parts by weight, 20 parts by weight, 20.5 parts by weight, 21 parts by weight, 21.5 parts by weight, 22 parts by weight,
22.5 parts by weight, 23 parts by weight, 23.5 parts by weight, 24 parts by weight, 24.5 parts by weight, 25 parts by weight, 25.5 parts by weight, 26 weight
Part, 26.5 parts by weight, 27 parts by weight, 27.5 parts by weight, 28 parts by weight, 28.5 parts by weight, 29 parts by weight, 29.5 parts by weight or 30
Parts by weight.
In the present invention, the temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than vertical
The fusing point of the compound polylactic acid of structure, preferably 150~180 DEG C, concretely 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C,
175 DEG C or 180 DEG C.
The present invention also provides a kind of preparations of polymethyl methacrylate heat-conductive composite material described in above-mentioned technical proposal
Method, comprising the following steps:
A) by polymethyl methacrylate, Poly L-lactic acid, poly- L-lactic acid and heat filling melt blending, poly- first is obtained
Base methyl acrylate heat-conductive composite material；
The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than the poly- cream of Stereocomplex type
The fusing point of acid.
In preparation method provided by the invention, first by polymethyl methacrylate, Poly L-lactic acid, poly- L-lactic acid
With heat filling melt blending in proportion.Wherein, it the polymethyl methacrylate, Poly L-lactic acid, poly- L-lactic acid and leads
Hot filler preferably before carrying out melting mixing, is first dried；The temperature of the drying is preferably 70~100 DEG C, specifically may be used
Think 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C；The time of the drying is preferably 1~5h, concretely
1h, 2h, 3h, 4h or 5h.In the present invention, the temperature of the melt blending is higher than the molten of Poly L-lactic acid and poly- L-lactic acid
Point, lower than the fusing point of Stereocomplex type polylactic acid, preferably 150~180 DEG C, concretely 150 DEG C, 155 DEG C, 160 DEG C, 165
DEG C, 170 DEG C, 175 DEG C or 180 DEG C；The melt blending preferably carries out under agitation, and the rate of the stirring is preferably 60
~100 revs/min, concretely 60 revs/min, 70 revs/min, 80 revs/min, 90 revs/min or 100 revs/min.In the present invention, it is preferred to
Using two step melt blendings, specifically include:
A1) by polymethyl methacrylate, Poly L-lactic acid and heat filling melt blending, melt is obtained；
A2) by the melt and poly- L-lactic acid melt blending.
In above-mentioned melt blending scheme provided by the invention, step a1) in melt blending time be preferably 5~
15min, concretely 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min；
Step a2) in time of melt blending be preferably 5~15min, concretely 5min, 6min, 7min, 8min, 9min, 10min,
11min, 12min, 13min, 14min or 15min.
After melt blending, blend melt is cooled down, and it is thermally conductive to obtain polymethyl methacrylate provided by the invention
Composite material.
Scheme provided by the invention prepares composite material of polymethyl methacrylate using watery fusion processing, such
Processing temperature section, Poly L-lactic acid and poly- L-lactic acid can melt completely, and only Stereocomplex type polylactic acid crystal can
With growth, since polylactic acid and polymethyl methacrylate have good compatibility, Stereocomplex type polylactic acid once being formed
Crystal will be dispersed in polylactic resin in the form of solid phase, the Stereocomplex type polylactic acid crystal pole being formed in situ
The big shearing force for improving melt, so that heat filling can be dispersed in matrix, so that effective passage of heat is formed,
It is further formed effective heat conduction network, and then improves the heating conduction of composite material.Meanwhile the present invention is by leading to adding
The specific type of hot filler optimizes screening, further improves the heating conduction of composite material.The experimental results showed that this
The thermal coefficient for inventing the heat-conductive composite material provided reaches as high as 4.1W/mK or more (GB/T 3399-1982).
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Raw material (polymethyl methacrylate, Poly L-lactic acid, the poly- right side used in the following embodiment and comparative examples of the present invention
Revolve lactic acid, heat filling) before carrying out melting mixing, it is firstly placed in 80 DEG C of vacuum oven and is dried, dry 3h.
Embodiment 1
Weigh 100 parts by weight of methyl methacrylate that poly- weight average molecular weight is 150,000, the poly- left side that weight average molecular weight is 10,000
Revolve 15 parts by weight of lactic acid, 2 parts by weight of aluminium nitride (partial size 800nm), two-dimentional 2 parts by weight of boron nitride nanosheet (partial size 50nm), oxygen
Change aluminium (partial size 500nm) 5 parts by weight；Above-mentioned raw materials are mixed into 5min under conditions of 180 DEG C, 80 revs/min, are added later
15 parts by weight of poly- L-lactic acid that weight average molecular weight is 10,000 mix 7min, are cooled to room temperature after blending, obtain polymethylacrylic acid
Methyl esters heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
1.63W/mK。
Embodiment 2
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 50,000, the poly- left side that weight average molecular weight is 10,000
Revolve 10 parts by weight of lactic acid, 5 parts by weight of aluminium nitride (partial size 1000nm), 5 parts by weight of aluminium vanadine (partial size 1200nm), silicon carbide (grain
Diameter 600nm) 2 parts by weight；Above-mentioned raw materials are mixed into 12min under conditions of 170 DEG C, 80 revs/min, adds divide equally again later
Son amount mixes 8min for 10,000 10 parts by weight of poly- L-lactic acid, is cooled to room temperature after blending, obtains polymethyl methacrylate
Heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
1.72W/mK。
Embodiment 3
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 100,000, the poly- left side that weight average molecular weight is 10,000
Revolve 2.5 parts by weight of lactic acid, 2.5 parts by weight of silver powder (partial size 1200nm), 2.5 parts by weight of silicon powder (partial size 800nm), superfine ceramic
2.5 parts by weight of powder (partial size 1500nm)；Above-mentioned raw materials are mixed into 8min under conditions of 170 DEG C, 80 revs/min, are added again later
Enter 2.5 parts by weight of poly- L-lactic acid that weight average molecular weight is 10,000 and mix 10min, is cooled to room temperature after blending, obtains poly- methyl-prop
E pioic acid methyl ester heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
2.41W/mK。
Embodiment 4
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 150,000, the poly- left side that weight average molecular weight is 50,000
Revolve 15 parts by weight of lactic acid, two-dimentional 5 parts by weight of boron nitride nanosheet (partial size 100nm), 5 weight of porous crystalline flake graphite (partial size 80nm)
Part, 5 parts by weight of silicon powder (partial size 1000nm)；Above-mentioned raw materials are mixed into 5min under conditions of 160 DEG C, 80 revs/min, later
It adds 15 parts by weight of poly- L-lactic acid that weight average molecular weight is 50,000 and mixes 5min, be cooled to room temperature after blending, obtain poly- methyl
Methyl acrylate heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
4.01W/mK。
Embodiment 5
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, two-dimentional 7.5 parts by weight of boron nitride nanosheet (partial size 150nm), 7.5 weight of aluminium nitride (partial size 1800nm)
Measure part, 7.5 parts by weight of silver powder (partial size 800nm), 7.5 parts by weight of silicon carbide (partial size 1500nm)；By above-mentioned raw materials 160 DEG C,
10min is mixed under conditions of 80 revs/min, is added 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and is mixed
15min is cooled to room temperature after blending, obtains polymethyl methacrylate heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
4.11W/mK。
Comparative example 1
100 parts by weight of polymethyl methacrylate that weight average molecular weight is 150,000 are weighed, in 180 DEG C, 80 revs/min of item
15min is mixed under part, is cooled to room temperature, un-added polymethyl methacrylate materials are obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained material, as a result are as follows: thermal coefficient 0.16W/
mK。
Comparative example 2
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 150,000, two-dimentional boron nitride nanosheet (partial size
120nm) 15 parts by weight, 15 parts by weight of boron nitride micro mist (partial size 1800nm)；By above-mentioned raw materials in 180 DEG C, 80 revs/min of item
15min is mixed under part, is cooled to room temperature after blending, and polymethyl methacrylate heat-conductive composite material is obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
0.61W/mK。
Comparative example 3
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 150,000, weight average molecular weight be 150,000 it is poly-
15 parts by weight of D-lactic acid, 10 parts by weight of silicon carbide (partial size 400nm), 10 parts by weight of aluminium nitride (partial size 1200nm)；It will be above-mentioned
Raw material mixes 15min under conditions of 180 DEG C, 80 revs/min, is cooled to room temperature after blending, obtains polymethyl methacrylate
Heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
0.57W/mK。
Comparative example 4
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 150,000, aluminium vanadine (partial size 1000nm) 12
Parts by weight, 12 parts by weight of alusil alloy powder (partial size 500nm)；Above-mentioned raw materials are mixed under conditions of 180 DEG C, 80 revs/min
5min adds 10 parts by weight of poly- L-lactic acid that weight average molecular weight is 50,000 later and mixes 10min, is cooled to room temperature after blending,
Obtain polymethyl methacrylate heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
0.65W/mK。
Comparative example 5
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, two-dimentional 10 parts by weight of boron nitride nanosheet (partial size 50nm)；By above-mentioned raw materials at 160 DEG C, 80 revs/min
10min is mixed under conditions of clock, is added 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and is mixed 15min,
It is cooled to room temperature after blending, obtains polymethyl methacrylate heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
1.34W/mK。
Comparative example 6
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, 10 parts by weight of aluminium nitride (partial size 800nm)；By above-mentioned raw materials in 160 DEG C, 80 revs/min of condition
Lower mixing 10min adds 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and mixes 15min, cold after blending
But to room temperature, polymethyl methacrylate heat-conductive composite material is obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
1.25W/mK。
Comparative example 7
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, 10 parts by weight of aluminium oxide (partial size 500nm)；By above-mentioned raw materials in 160 DEG C, 80 revs/min of condition
Lower mixing 10min adds 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and mixes 15min, cold after blending
But to room temperature, polymethyl methacrylate heat-conductive composite material is obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
1.07W/mK。
Comparative example 8
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, two-dimentional 30 parts by weight of boron nitride nanosheet (partial size 150nm)；By above-mentioned raw materials 160 DEG C, 80 turns/
10min is mixed under conditions of minute, 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 is added later and mixes
15min is cooled to room temperature after blending, obtains polymethyl methacrylate heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
3.85W/mK。
Comparative example 9
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, 30 parts by weight of aluminium nitride (partial size 1800nm)；By above-mentioned raw materials in 160 DEG C, 80 revs/min of condition
Lower mixing 10min adds 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and mixes 15min, cold after blending
But to room temperature, polymethyl methacrylate heat-conductive composite material is obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
2.91W/mK。
Comparative example 10
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, 30 parts by weight of silver powder (partial size 800nm)；By above-mentioned raw materials under conditions of 160 DEG C, 80 revs/min
10min is mixed, 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 is added later and mixes 15min, it is cooling after blending
To room temperature, polymethyl methacrylate heat-conductive composite material is obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
3.04W/mK。
Comparative example 11
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, 32 parts by weight of silicon carbide (partial size 1500nm)；By above-mentioned raw materials in 160 DEG C, 80 revs/min of condition
Lower mixing 10min adds 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and mixes 15min, cold after blending
But to room temperature, polymethyl methacrylate heat-conductive composite material is obtained.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
2.32W/mK。
Comparative example 12
Weigh 100 parts by weight of polymethyl methacrylate that weight average molecular weight is 200,000, weight average molecular weight be 200,000 it is poly-
11 parts by weight of D-lactic acid, two-dimentional 7.5 parts by weight of boron nitride nanosheet (partial size 150nm), 7.5 weight of aluminium nitride (partial size 1800nm)
Measure part, 7.5 parts by weight of silver powder (partial size 800nm), 7.5 parts by weight of silicon carbide (partial size 1500nm)；By above-mentioned raw materials 200 DEG C,
10min is mixed under conditions of 80 revs/min, is added 11 parts by weight of poly- L-lactic acid that weight average molecular weight is 200,000 later and is mixed
15min is cooled to room temperature after blending, obtains polymethyl methacrylate heat-conductive composite material.
Heating conduction measurement (GB/T 31402-2015) is carried out to obtained heat-conductive composite material, as a result are as follows: thermal coefficient
1.2W/mK。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of polymethyl methacrylate heat-conductive composite material, by the raw material melt blending system including following parts by weight of component
At:
The heat filling include two-dimentional boron nitride nanosheet, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramic powder, silver powder,
At least three kinds in silicon powder, alusil alloy powder and porous crystalline flake graphite；
The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than Stereocomplex type polylactic acid
Fusing point.
2. composite material according to claim 1, which is characterized in that the partial size of the heat filling is 50~2000nm.
3. composite material according to claim 1, which is characterized in that the heat filling includes two-dimentional boron nitride nanometer
Three kinds in piece, aluminium oxide, silicon carbide, aluminium nitride, aluminium vanadine, ceramic powder, silver powder, silicon powder and porous crystalline flake graphite or four kinds.
4. composite material according to claim 1, which is characterized in that the weight average molecular weight of the polymethyl methacrylate
It is 5~200,000.
5. composite material according to claim 1, which is characterized in that the weight average molecular weight of the Poly L-lactic acid be 1~
200000.
6. composite material according to claim 1, which is characterized in that the weight average molecular weight of the poly- L-lactic acid be 1~
200000.
7. composite material according to claim 1, which is characterized in that the quality of the Poly L-lactic acid and poly- L-lactic acid
Than for 1:(0.5~2).
8. a kind of preparation method of any one of claim 1~7 polymethyl methacrylate heat-conductive composite material, including with
Lower step:
A) by polymethyl methacrylate, Poly L-lactic acid, poly- L-lactic acid and heat filling melt blending, poly- methyl-prop is obtained
E pioic acid methyl ester heat-conductive composite material；
The temperature of the melt blending is higher than the fusing point of Poly L-lactic acid and poly- L-lactic acid, lower than Stereocomplex type polylactic acid
Fusing point.
9. preparation method according to claim 8, which is characterized in that in step a), the detailed process of the melt blending
Include:
A1) by polymethyl methacrylate, Poly L-lactic acid and heat filling melt blending, melt is obtained；
A2) by the melt and poly- L-lactic acid melt blending, polymethyl methacrylate heat-conductive composite material is obtained.
10. preparation method according to claim 9, which is characterized in that step a1) described in the temperature of melt blending be
150~180 DEG C, the time is 5~15min；
Step a2) described in melt blending temperature be 150~180 DEG C, the time be 5~15min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111205579A (en) * | 2020-02-22 | 2020-05-29 | 杭州电子科技大学 | High-efficiency high-temperature-resistant aluminum nitride/polymer composite material and preparation method thereof |
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| CN101735582A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Poly(lactic acid)/poly(methyl methacrylate) alloy material and preparation method thereof |
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| CN101735582A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Poly(lactic acid)/poly(methyl methacrylate) alloy material and preparation method thereof |
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