CN109880281A - A kind of activeness and quietness polyformaldehyde composite material and preparation method thereof - Google Patents
A kind of activeness and quietness polyformaldehyde composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of activeness and quietness polyformaldehyde (POM) composite material and preparation methods, belong to field of high polymer material modification.The activeness and quietness polyformaldehyde composite material is made of: POM:500-640 parts following weight fraction component；TPU:200-470 parts；Nano redigity particle: 20-40 parts；Coupling agent: 1-2.2 parts；Antioxidant: 5-10 parts.The present invention improves the rigidity of POM material using nano inorganic rigid particles, simultaneously by TPU toughening POM to keep its toughness, to obtain the polyformaldehyde composite material of high-intensitive and high tenacity, particularly suitable for fields such as industrial machinery, auto parts and components, engineering structure parts.
Description
Technical field
The present invention relates to polymer modification field, in particular to a kind of activeness and quietness polyformaldehyde composite material and its system
Preparation Method.
Background technique
Polyformaldehyde (POM) is one kind using [- CH2-O-] n as the polymer of main chain, with high crystalline, high intensity, low compacted
Become, excellent dimensional stability the features such as, and have the characteristics of outstanding self-lubrication and high-wearing feature, be highly suitable for work
The close part such as industry gear, bearing, buckle, can replace the metals such as copper, zinc, lead, be applied to industrial machinery, auto parts, essence
The fields such as close instrument, electronic apparatus are commonly called as match steel.
As the polyformaldehyde of one of five big general engineering plastics, be in all plastics specific strength and specific stiffness close to metal
One of resin variety, this is also just being derived from its plurality of advantages: high strength and stiffness, and good dimensional stability is excellent
Rotproofness, wear-resisting, self-lubricating and creep-resistant property, noiseless, endurance, critical PV value is high, and machine-shaping is convenient, raw material valence
It is honest and clean to be easy to get, occupy critical positions in new structural material, but it is only drawback is that have that toughness is not high.To improve
The performance of polyformaldehyde extends the application field of polyformaldehyde, need by polyformaldehyde by physics appropriate, chemical means with it is corresponding
Substance is compounded to form modified polyformaldehyde composite material.But if carrying out toughening to it with elastomer, though toughness can change
It is kind, but have lost the rigidity of material preciousness.
To find out its cause, the simple regularity of POM molecular chain structure is high and unbranched, therefore its crystallinity is very high, crystallization speed
Degree is fast, but also making its crystal size greatly causes notch shock poor, and high to notch sensitive, residual internal stress.In order to improve
POM toughness, most common method are exactly thermoplastic polyurethane (TPU) blending and modifying, can by the way that suitable TPU material is added
To increase substantially the impact strength of POM, but the rigidity of POM is also reduced simultaneously, therefore significantly limit answering for toughening POM
With.
Summary of the invention
For above-mentioned technological difficulties of the existing technology, the present invention provides a kind of activeness and quietness polyformaldehyde composite materials
And preparation method thereof, it is blended by introducing the particle-filled POM of nano redigity, then with TPU, superhigh tenacity has successfully been obtained, simultaneously
Guarantee the rigidity of POM material, to obtain high-intensitive and high tenacity polyformaldehyde composite material.
The technical solution is as follows:
On the one hand, a kind of activeness and quietness polyformaldehyde composite material is provided, by following weight fraction at being grouped as:
POM:500-640 parts,
TPU:200-470 parts,
Nano redigity particle: 20-40 parts,
Coupling agent: 1-2.2 parts,
Antioxidant: 5-10 parts.
Further, the activeness and quietness polyformaldehyde composite material, by following weight fraction at being grouped as:
POM:550-620 parts,
TPU:270-415 parts,
Nano redigity particle: 35-40 parts,
Coupling agent: 1.5-2.2 parts,
Antioxidant: 6.5-10 parts.
Further, the POM is copolymerization POM or homopolymerization POM.
Further, the TPU is polyether polyurethane elastomer, Shao A hardness≤85A.
Further, the nano redigity particle is nanometer calcium sulfate whisker, nanometer calcium carbonate powder, nano oxidized silicon powder
Body, it is nano alumina powder jointed in any one or they any one combination.
Further, the coupling agent is silane coupling agent.
On the other hand, a kind of preparation method of activeness and quietness polyformaldehyde composite material is provided, comprising:
First by POM, nano redigity particle, coupling agent, that antioxidant is proportionally added into high-speed mixer and mixing is uniform；
The particle-filled POM master batch of nano redigity is obtained by double screw extruder extruding pelletization；
It is again that POM master batch and TPU addition high-speed mixer and mixing is uniform, then obtained by double screw extruder extruding pelletization
Activeness and quietness polyformaldehyde composite material.
Further, POM, nano redigity particle, coupling agent, antioxidant are proportionally added into high mixer at 70-90 DEG C
Lower to be uniformly mixed, for each section of double screw extruder used controlled at 160-200 DEG C, screw speed is set as 240-
260rpm。
Further, POM, nano redigity particle, coupling agent, antioxidant are proportionally added into high mixer and are mixed at 80 DEG C
It closes uniform.
Technical solution provided in an embodiment of the present invention has the benefit that
Activeness and quietness polyformaldehyde composite material provided in an embodiment of the present invention, by addition nano redigity particle to POM into
Row activeness and quietness is modified, adds toughener TPU and further carries out toughening to POM, to obtain high impact and toughness
POM material, while improving the problem of toughening POM material stiffness reduces；On the other hand, the activeness and quietness that inventive embodiments provide
Polyformaldehyde composite material preparation method, by fabricating in two steps, guarantee nano redigity particle is preferentially entered in POM matrix,
Guarantee that material is able to maintain its rigidity while increasing toughness.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Activeness and quietness polyformaldehyde (POM, Paraformaldehyde) composite material provided in an embodiment of the present invention, due to
The bending strength of toughening POM, bending modulus can be improved in nano-particles filled POM, by addition nano redigity particle to POM into
Row activeness and quietness is modified, adds toughener TPU (thermoplastic polyurethane elastomer rubber, Thermoplastic
Polyurethanes toughening further) is carried out to POM, to obtain high impact and toughness, while improving toughening POM
The problem of material stiffness reduces；On the other hand, the activeness and quietness polyformaldehyde composite material preparation method that inventive embodiments provide is led to
It is fabricated after in two steps, guarantees that nano redigity particle preferentially enters in POM matrix, to guarantee that material has been able to maintain it just
Property, therefore the polyformaldehyde composite material of this high-intensity and high-tenacity, particularly suitable for industrial machinery, auto parts and components, work
The fields such as journey structural member.
It should be noted that raw materials used in embodiment: POM is 500P (E.I.Du Pont Company, homopolymerization type), TPU 7560
(COIM company, polyether-type, Shao A hardness 70), rigid particles used are nano silica powder (nano-SiO2It is commercially available), it is used
Coupling agent is KH560.
Embodiment 1
The specific weight fraction proportion of each component is POM500P:640 parts, TPU7560:320 parts, nano-SiO2: 40
Part, KH560:2.2 parts, antioxidant: 8 parts.First by POM, nano-SiO2, that high speed is added in KH560, antioxidant according to the above ratio is mixed
It is uniformly mixed at 80 DEG C in conjunction machine, is then filled uniformly mixed material by double screw extruder extruding pelletization
Master batch, each section set temperature of extruder temperature are as follows: 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200
DEG C, 200 DEG C, 190 DEG C, screw speed is set as 240rpm.Filler parent granule and TPU are uniformly mixed in a high speed mixer again
Afterwards, activeness and quietness polyformaldehyde product is obtained by double screw extruder extruding pelletization, each section of extruder temperature is set as 160
DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed is set as
240rpm。
Embodiment 2
The specific weight fraction proportion of each component is POM500P:500 parts, TPU7560:470 parts, nano-SiO2: 30
Part, KH560:1 parts, antioxidant: 5 parts.First by POM, nano-SiO2, KH560, antioxidant mixed at high speed is added according to the above ratio
It is uniformly mixed at 80 DEG C in machine, it is female then to be obtained into filling by double screw extruder extruding pelletization for uniformly mixed material
Grain, extruder temperature set each section be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C,
200 DEG C, 190 DEG C, screw speed is set as 240rpm.Again in a high speed mixer after mixing by filler parent granule and TPU, lead to
Cross double screw extruder extruding pelletization obtain product, each section of extruder temperature be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed is set as 240rpm.
Embodiment 3
The specific weight fraction proportion of each component is POM500P:620 parts, TPU7560:290 parts, nano-SiO2: 20
Part, KH560:1.5 parts, antioxidant: 8.5 parts.First by POM, nano-SiO2, KH560, antioxidant high speed is added according to the above ratio
It is uniformly mixed at 70 DEG C in mixing machine, is then filled out uniformly mixed material by double screw extruder extruding pelletization
Fill master batch, each section of extruder temperature be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C,
200 DEG C, 190 DEG C, screw speed is set as 251rpm.Again in a high speed mixer after mixing by filler parent granule and TPU, lead to
Cross double screw extruder extruding pelletization and obtain product, each section of extruder temperature setting 160,180,180,180,180,185,
185,200,200,190 DEG C, screw speed is set as 240rpm.
Embodiment 4
The specific weight fraction proportion of each component is POM500P:580 parts, TPU7560:390 parts, nano-SiO2: 30
Part, KH560:1.5 parts, antioxidant: 6.5 parts.First by POM, nano-SiO2, KH560, antioxidant high speed is added according to the above ratio
It is uniformly mixed at 90 DEG C in mixing machine, is then filled out uniformly mixed material by double screw extruder extruding pelletization
Fill master batch, each section of extruder temperature be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C,
200 DEG C, 190 DEG C, screw speed is set as 260rpm.Again in a high speed mixer after mixing by filler parent granule and TPU, lead to
Cross double screw extruder extruding pelletization obtain product, each section of extruder temperature be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed is set as 240rpm.
Comparative example 1
The specific weight fraction proportion of each component is POM500P:600 parts, TPU7560:400 parts, antioxidant: 7 parts.It will
POM and TPU, antioxidant in a high speed mixer in 80 DEG C after mixing, produced by double screw extruder extruding pelletization
Product, each section of extruder temperature are set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200
DEG C, 190 DEG C, screw speed is set as 240rpm.
Comparative example 2
The specific weight fraction proportion of each component is POM500P:580 parts, TPU7560:390 parts, nano-SiO2: 30
Part, KH560:1.5 parts, antioxidant: 7 parts.By POM, TPU and nano-SiO2, KH560, antioxidant be added high-speed mixer in
It is uniformly mixed at 70 DEG C, uniformly mixed material is then obtained into product, extruder temperature by double screw extruder extruding pelletization
It spends each section and is set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, spiral shell
Bar revolving speed is set as 251rpm.
Test result is as follows for embodiment and comparative example shown in table 1, and wherein testing standard is ASTM standard.
1 embodiment 1-4 of table and comparative example 1-2 test result
Comparative example 1-4 and comparative example 1, it is found that bending strength, bending modulus and the impact of embodiment 1-4 is by force
Three indexs are spent obviously higher than comparative example 1, this is because the POM material of the non-plus nano rigid particles of comparative example 1, although punching
Hit intensity is preferable, but material bending intensity and modulus is lower, and material is partially soft.Comparative example 1-4 and comparative example 2, embodiment 1-4
Three indexs be also apparently higher than comparative example 2, although comparative example 2 also joined nano redigity particle, received in extrusion process
Rice rigid particles can enter in POM and TPU simultaneously, and nano redigity particle can play the role of activeness and quietness in POM, but
The toughening effect of TPU can be destroyed in TPU.And the embodiment of the present invention is by two one-step extrusion moldings, all nano redigity particles are first
It is mixed into POM, then extruding pelletization, it is ensured that nano redigity particle preferentially enters POM inside ensuring and plays toughening enhancing to POM
Effect.According to above-mentioned test result can be seen that activeness and quietness polyformaldehyde composite material formula provided in an embodiment of the present invention and
Preparation method can obtain the POM material of superhigh tenacity and high impact, and bending strength and bending modulus are also obvious
Higher than commercially available high tenacity POM, illustrate that its toughness is also more preferable.
Embodiment 5
The specific weight fraction proportion of each component is POM500P:550 parts, and TPU7560:415 parts, nanometer calcium sulfate is brilliant
Must: 10 parts, nano-SiO2: 25 parts, KH560:1.5 parts, antioxidant: 6.5 parts.First by POM, nanometer calcium sulfate whisker, nano-
SiO2, KH560, antioxidant be added in high-speed mixer and be uniformly mixed at 80 DEG C according to the above ratio, then will be uniformly mixed
Material obtains filler parent granule by double screw extruder extruding pelletization, and extruder temperature sets each section and is set as 160 DEG C, 180
DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed is set as 240rpm.Again will
Filler parent granule and TPU after mixing, pass through double screw extruder extruding pelletization and obtain product, extruder in a high speed mixer
Each section of temperature be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C,
Screw speed is set as 240rpm.
Embodiment 6
POM500P:620 parts, TPU7560:360 parts, nanometer calcium sulfate whisker: 10 parts, nanometer calcium carbonate powder: 10 parts,
KH560:2.2 parts, antioxidant: 8 parts.First by POM, nanometer calcium sulfate whisker, nanometer calcium carbonate powder, KH560, antioxidant by upper
It states and is uniformly mixed at 70 DEG C in ratio addition high-speed mixer, then squeeze uniformly mixed material by double screw extruder
Be granulated out and obtain filler parent granule, each section of extruder temperature set 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C,
185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed be set as 240rpm.Again in a high speed mixer by filler parent granule and TPU
After mixing, product is obtained by double screw extruder extruding pelletization, each section of extruder temperature set 160 DEG C, 180 DEG C,
180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed be set as 240rpm.
Embodiment 7
POM500P:620 parts, TPU7560:270 parts, nanometer calcium carbonate powder: 30 parts, nano alumina powder jointed: 10 parts,
KH560:1.5 parts, antioxidant: 10 parts.First POM, nanometer calcium carbonate powder, nano alumina powder jointed, KH560, antioxidant are pressed
Aforementioned proportion is added in high-speed mixer and is uniformly mixed at 80 DEG C, and uniformly mixed material is then passed through double screw extruder
Extruding pelletization, obtains filler parent granule, and each section of extruder temperature sets 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185
DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed be set as 248rpm.Again by filler parent granule and TPU in high-speed mixer
In after mixing, product is obtained by double screw extruder extruding pelletization, each section of extruder temperature is set as 160 DEG C, 180
DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed be set as 240rpm.
Embodiment 8
POM500P:600 parts, TPU7560:350 parts, nano-SiO2: 20 parts, nanometer calcium sulfate whisker: 10 parts, nano-sized carbon
Sour calcium powder body: 10 parts, KH560:1.5 parts, antioxidant: 8 parts.First by POM, nanometer calcium sulfate whisker, nanometer calcium carbonate powder,
Nano-SiO2, KH560, antioxidant are added according to the above ratio in high-speed mixer to be uniformly mixed at 90 DEG C, then will be mixed equal
Even material obtains filler parent granule by double screw extruder extruding pelletization, and each section of extruder temperature is set as fixed 160 DEG C, 180
DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, screw speed be set as 260rpm.Again will
Filler parent granule and TPU after mixing, pass through double screw extruder extruding pelletization and obtain product, extruder in a high speed mixer
Each section of temperature be set as 160 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 200 DEG C, 200 DEG C, 190 DEG C,
Screw speed is set as 240rpm.
2 embodiment 5-8 test result of table
It is found by comparing the test result of embodiment 1-4 in embodiment 5-8 test result in table 2 and table 1, embodiment
The performance indexes of 5-8 material prepared is further increased compared with embodiment 1-4.This explanation by two kinds of nano redigity particles into
Row compounding can play certain collaboration improvement result, availability more preferably activeness and quietness POM material.
In conclusion activeness and quietness polyformaldehyde composite material provided in an embodiment of the present invention, by adding nano redigity grain
Son carries out activeness and quietness to POM and is modified, and adds toughener TPU and further carries out toughening to POM, to obtain high impact
With the POM material of toughness, while improve toughening POM material stiffness reduce the problem of；On the other hand, inventive embodiments provide
Activeness and quietness polyformaldehyde composite material preparation method guarantees that nano redigity particle preferentially enters POM by fabricating in two steps
In matrix, its rigidity can be kept well while improving toughness of material.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of activeness and quietness polyformaldehyde composite material, which is characterized in that by following weight fraction at being grouped as:
POM:500-640 parts,
TPU:200-470 parts,
Nano redigity particle: 20-40 parts,
Coupling agent: 1-2.2 parts,
Antioxidant: 5-10 parts.
2. activeness and quietness polyformaldehyde composite material according to claim 1, which is characterized in that by following weight fraction ingredient
Composition:
POM:550-620 parts,
TPU:270-415 parts,
Nano redigity particle: 35-40 parts,
Coupling agent: 1.5-2.2 parts,
Antioxidant: 6.5-10 parts.
3. activeness and quietness polyformaldehyde composite material according to claim 1 or 2, which is characterized in that the POM is copolymerization
POM or homopolymerization POM.
4. activeness and quietness polyformaldehyde composite material according to claim 1 or 2, which is characterized in that the TPU is polyether-type
Polyurethane elastomer, Shao A hardness≤85A.
5. activeness and quietness polyformaldehyde composite material according to claim 1 or 2, which is characterized in that the nano redigity grain
Son be nanometer calcium sulfate whisker, nanometer calcium carbonate powder, nano silica powder, it is nano alumina powder jointed in any one or
Their any one combination.
6. activeness and quietness polyformaldehyde composite material according to claim 1 or 2, which is characterized in that the coupling agent is silicon
Alkane coupling agent.
7. a kind of preparation method of such as activeness and quietness polyformaldehyde composite material as claimed in any one of claims 1 to 6, feature exist
In, comprising:
First by POM, nano redigity particle, coupling agent, that antioxidant is proportionally added into high-speed mixer and mixing is uniform；
The particle-filled POM master batch of nano redigity is obtained by double screw extruder extruding pelletization；
It is again that POM master batch and TPU addition high-speed mixer and mixing is uniform, then enhanced by double screw extruder extruding pelletization
Reinforced polyformaldehyde composite material.
8. preparation method according to claim 7, which is characterized in that by POM, nano redigity particle, coupling agent, antioxidant
It is proportionally added into high mixer and is uniformly mixed at 70-90 DEG C, each section of double screw extruder used is controlled at 160-200
DEG C, screw speed is set as 240-260rpm.
9. preparation method according to claim 8, which is characterized in that by POM, nano redigity particle, coupling agent, antioxidant
It is proportionally added into high mixer and is uniformly mixed at 80 DEG C.
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