CN106118036A - A kind of light-sensitive material containing PVC and PS and preparation method thereof - Google Patents

A kind of light-sensitive material containing PVC and PS and preparation method thereof Download PDF

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Publication number
CN106118036A
CN106118036A CN201610613011.6A CN201610613011A CN106118036A CN 106118036 A CN106118036 A CN 106118036A CN 201610613011 A CN201610613011 A CN 201610613011A CN 106118036 A CN106118036 A CN 106118036A
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Prior art keywords
sensitive material
light
granule
preparation
pvc
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CN201610613011.6A
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Inventor
博尔金海伦
张凌竹
塔林
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Plastic Forming Technology (beijing) Co Ltd
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Plastic Forming Technology (beijing) Co Ltd
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Priority to CN201610613011.6A priority Critical patent/CN106118036A/en
Publication of CN106118036A publication Critical patent/CN106118036A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention relates to a kind of light-sensitive material containing PVC and PS, and preparation method thereof, described light-sensitive material be PS granule and PVC granule are dissolved in the mixed solution of IBOA, HDDA, TPGDA, LA, SMA stirring after, then the light-sensitive material obtained after adding resin;Described light-sensitive material is the liquid photosensitive resin for preparing plastic;The elastic modulus E of described light-sensitive material test is 3.0 3.25GPa.After the compositional refinements of the present invention, solid-state light-sensitive material after polymerization has the mechanical characteristic of all types of plastic goods, especially there is splendid elastic modelling quantity, hot strength, heat-resisting quantity, density of material, it is possible to meet the performance requirement to plastic in various application scenario.

Description

A kind of light-sensitive material containing PVC and PS and preparation method thereof
Technical field
The present invention relates to resin material and preparation method thereof, be specifically related to a kind of light-sensitive material containing PVC and PS and Preparation method.
Background technology
Nineteen sixty-eight, Bayer A.G developed the first generation uv curing coating of polyester/polystyrene systems, opened light The gate of curing technology industry, along with science and technology development, photocuring technology application from printing plate the earliest, photoresist development to Photocureable coating, ink, adhesive, application constantly expand.3D prints the emerging field applied as this technology, has had Certain application range, photosensitive resin prints raw material as photocuring 3D, and its liquid photosensitive resin raw material causes through illumination to be handed over Solidification solid is formed after connection solidification.Traditional photosensitive resin, after allotment photocuring, does not have the power of various plastic Learn characteristic, there is many shortcomings.Routine use cannot be met.
Photosensitive resin formulation is simply simply allocated by prior art, and after not solidifying it, mechanical property provides concrete Test, the performance of the plastic product after its solidification can not meet multiple requirement.After liquid photosensitive resin aggregates into solid-state, do not have There is the mechanical characteristic of present all types of plastic goods, such as poor tensile strength, the yielding decomposition of high temperature, the flexible shortcoming such as poor, frangible.
Summary of the invention
It is an object of the invention to overcome defect of the prior art, design a kind of light-sensitive material containing PVC and PS and Its preparation method, after the compositional refinements of the present invention, the mechanics that the solid-state light-sensitive material after polymerization has all types of plastic goods is special Property, especially has splendid elastic modelling quantity, hot strength, heat-resisting quantity, density of material, it is possible to it is right to meet in various application scenario The performance requirement of plastic.
For achieving the above object, the technical solution adopted in the present invention is a kind of light-sensitive material containing PVC and PS, described Light-sensitive material be PS granule and PVC granule are dissolved in the mixed solution of IBOA, HDDA, TPGDA, LA, SMA stirring after, then The light-sensitive material obtained after adding resin;Described light-sensitive material is the liquid photosensitive resin for preparing plastic;Described light The elastic modulus E of quick testing of materials is 3.0-3.25GPa, has splendid mechanical property, it is possible to meet the plastics that resin-made is standby The mechanical property requirements of goods.
The present invention discloses the preparation method of a kind of light-sensitive material containing PVC and PS, the step of described preparation method Suddenly it is:
(1) monomer IBOA, HDDA, TPGDA, LA, SMA are sequentially added into mix homogeneously in stirred tank;
(2) in stirred tank, PS granule and PVC granule are added;
(3) heated and stirred still, stirring simultaneously makes PS granule and PVC granule be completely dissolved;
(4) adding resin in reactor, heated and stirred still stirs simultaneously, and material stirring is uniform;
(5) described light-sensitive material is obtained after standing;Time of repose is 48 hours.
(6) take step gained light-sensitive material and use 3D printer draws a design whether test product according to GB/T 1040-92 standard Qualified.
Preferably, in step (1), the volume mixture ratio of 5 kinds of monomers is 2:2:(0.5-1.5): (2-4): (0.5-1.5).
Preferably, the PS granule added in step (2) and the volume ratio of PVC granule are 2:(0.5-1.5);PS granule and The volume summation of PVC granule is (0.5-2) with the ratio of the volume summation of five kinds of monomers IBOA, HDDA, TPGDA, LA, SMA: 12.
Preferably, in step (3), the temperature of heated and stirred still is 37-43 DEG C, and the rotating speed of stirring is 85-115 rev/min, Mixing time is 38-58 hour.
Preferably, the resin added in step (4) is urethane acrylate, urethane acrylate, epoxy acrylic Ester and the mixture of polyester acrylate.
Preferably, the mass ratio of existing material is 7:(2-to the quality of the resin added in step (4) with reactor 4).
Preferably, urethane acrylate, urethane acrylate, epoxy acrylic in the resin added in step (4) The volume ratio of ester and polyester acrylate is (1.5-2.5): (1-2): (1.5-2.5): 1.
Preferably, in step (4), the temperature of heated and stirred still is 53-67 DEG C, and the rotating speed of stirring is 85-115 rev/min, Mixing time is 8-16 hour.
It is further preferred that the volume mixture ratio of 5 kinds of monomers is 2:2:1:3:1 in step (1);
Urethane acrylate, urethane acrylate, epoxy acrylate and polyester in the resin added in step (4) The volume ratio of acid esters is 2:1.5:2:1.
Advantages of the present invention and having the beneficial effects that:
After the compositional refinements of the present invention, the solid-state light-sensitive material after polymerization has the mechanical characteristic of all types of plastic goods, especially There is splendid elastic modelling quantity, hot strength, heat-resisting quantity, density of material, it is possible to meet in various application scenario plastics system The performance requirement of product.
The test result of its Elastic Modulus is 3.0-3.25GPa;Hot strength reaches 40Mpa;Without substantially during 170 DEG C of stress Deformation;Density is 0.96g/m;There is the performance of excellence.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described.Following example are only used for more Add and clearly demonstrate technical scheme, and can not limit the scope of the invention with this.
Embodiment 1
The present embodiment is the preparation method of the light-sensitive material containing PVC and PS, and the step of preparation method is:
(1) monomer IBOA, HDDA, TPGDA, LA, SMA are sequentially added into mix homogeneously in stirred tank;The volume mixture of 5 kinds of monomers Ratio is 2:2:1:3:1.
(2) in stirred tank, PS granule and PVC granule are added;
The PS granule added in step (2) and the volume ratio of PVC granule are 2:1;The volume summation and five of PS granule and PVC granule The ratio of the volume summation planting monomer IBOA, HDDA, TPGDA, LA, SMA is 1:12.
(3) heated and stirred still, stirring simultaneously makes PS granule and PVC granule be completely dissolved;The temperature of heated and stirred still is 40 DEG C, the rotating speed of stirring is 100 revs/min, and mixing time is 48 hours.
(4) adding resin in reactor, heated and stirred still stirs simultaneously, and material stirring is uniform;The resin added The mass ratio of existing material is 7:3 to quality with reactor.
Urethane acrylate, urethane acrylate, epoxy acrylate and polyester acrylate in the resin added Volume ratio be 2:1.5:2:1.
The temperature of heated and stirred still is 60 DEG C, and the rotating speed of stirring is 100 revs/min, and mixing time is 12 hours.
(5) described light-sensitive material is obtained after standing;Time of repose is 48 hours.
(6) take step gained light-sensitive material and use 3D printer draws a design whether test product according to GB/T 1040-92 standard Qualified.
Test product step (6) prepared, carries out performance test as follows:
A, Mechanics Performance Testing;Equipment: electronic universal tester.The test result of elastic modelling quantity is 3.25GPa.
B, Mechanics Performance Testing;Equipment: electronic universal tester.The test result of hot strength is 40Mpa
C, thermo-mechanical analysis: equipment oven heat, counterweight.Counterweight is hung, without substantially becoming when being heated to 170 DEG C of stress in product lower end Shape.
D, density measure: powder specific weight determine.The density of product test is 0.96g/m.
It follows that the solid-state light-sensitive material after the polymerization prepared of the present embodiment has preferable mechanical characteristic, especially have There are splendid elastic modelling quantity, hot strength, heat-resisting quantity, density of material, it is possible to meet in various application scenario plastic Performance requirement.
Embodiment 2
The preparation method of the light-sensitive material containing PVC and PS, the step of preparation method is:
(1) monomer IBOA, HDDA, TPGDA, LA, SMA are sequentially added into mix homogeneously in stirred tank;The volume mixture of 5 kinds of monomers Ratio is 2:2:0.5:4:0.5.
(2) in stirred tank, PS granule and PVC granule are added;
The PS granule added in step (2) and the volume ratio of PVC granule are 2:0.5;The volume summation of PS granule and PVC granule with The ratio of the volume summation of five kinds of monomers IBOA, HDDA, TPGDA, LA, SMA is 2:12.
(3) heated and stirred still, stirring simultaneously makes PS granule and PVC granule be completely dissolved;The temperature of heated and stirred still is 37 DEG C, the rotating speed of stirring is 115 revs/min, and mixing time is 58 hours.
(4) adding resin in reactor, heated and stirred still stirs simultaneously, and material stirring is uniform;The resin added The mass ratio of existing material is 7:2 to quality with reactor.
Urethane acrylate, urethane acrylate, epoxy acrylate and polyester acrylate in the resin added Volume ratio be 1.5:2:1.5:1.
The temperature of heated and stirred still is 53 DEG C, and the rotating speed of stirring is 115 revs/min, and mixing time is 16 hours.
(5) described light-sensitive material is obtained after standing;Time of repose is 48 hours.
(6) take step gained light-sensitive material and use 3D printer draws a design whether test product according to GB/T 1040-92 standard Qualified.
Embodiment 3
The preparation method of the light-sensitive material containing PVC and PS, the step of preparation method is:
(1) monomer IBOA, HDDA, TPGDA, LA, SMA are sequentially added into mix homogeneously in stirred tank;The volume mixture of 5 kinds of monomers Ratio is 2:2:1.5:2:1.5.
(2) in stirred tank, PS granule and PVC granule are added;
The PS granule added in step (2) and the volume ratio of PVC granule are 2:1.5;The volume summation of PS granule and PVC granule with The ratio of the volume summation of five kinds of monomers IBOA, HDDA, TPGDA, LA, SMA is 0.5:12.
(3) heated and stirred still, stirring simultaneously makes PS granule and PVC granule be completely dissolved;The temperature of heated and stirred still is 43 DEG C, the rotating speed of stirring is 85 revs/min, and mixing time is 38 hours.
(4) adding resin in reactor, heated and stirred still stirs simultaneously, and material stirring is uniform;The resin added The mass ratio of existing material is 7:4 to quality with reactor.
Urethane acrylate, urethane acrylate, epoxy acrylate and polyester acrylate in the resin added Volume ratio be 2.5:1:2.5:1.
The temperature of heated and stirred still is 67 DEG C, and the rotating speed of stirring is 85 revs/min, and mixing time is 8 hours.
(5) described light-sensitive material is obtained after standing;Time of repose is 48 hours.
(6) take step gained light-sensitive material and use 3D printer draws a design whether test product according to GB/T 1040-92 standard Qualified.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For Yuan, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvements and modifications, these improvements and modifications Also should be regarded as protection scope of the present invention.

Claims (10)

1. the light-sensitive material containing PVC and PS, it is characterised in that described light-sensitive material is by molten to PS granule and PVC granule After solution stirs in the mixed solution of IBOA, HDDA, TPGDA, LA, SMA, then the light-sensitive material obtained after adding resin;
Described light-sensitive material is the liquid photosensitive resin for preparing plastic;
The elastic modulus E of described light-sensitive material test is 3.0-3.25GPa.
2. the preparation method preparing the light-sensitive material containing PVC and PS as claimed in claim 1, it is characterised in that institute The step stating preparation method is:
(1) monomer IBOA, HDDA, TPGDA, LA, SMA are sequentially added into mix homogeneously in stirred tank;
(2) in stirred tank, PS granule and PVC granule are added;
(3) heated and stirred still, stirring simultaneously makes PS granule and PVC granule be completely dissolved;
(4) adding resin in reactor, heated and stirred still stirs simultaneously, and material stirring is uniform;
(5) described light-sensitive material is obtained after standing;
(6) take step gained light-sensitive material use 3D printer according to GB/T 1040-92 standard draw a design test product whether close Lattice.
3. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 2, it is characterised in that in step (1) 5 The volume mixture ratio planting monomer is 2:2:(0.5-1.5): (2-4): (0.5-1.5).
4. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 2, it is characterised in that step adds in (2) The PS granule added and the volume ratio of PVC granule are 2:(0.5-1.5);The volume summation of PS granule and PVC granule and five kinds of monomers The ratio of the volume summation of IBOA, HDDA, TPGDA, LA, SMA is (0.5-2): 12.
5. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 2, it is characterised in that step adds in (3) The temperature of thermal agitation still is 37-43 DEG C, and the rotating speed of stirring is 85-115 rev/min, and mixing time is 38-58 hour.
6. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 2, it is characterised in that step adds in (4) The resin entered is the mixture of urethane acrylate, urethane acrylate, epoxy acrylate and polyester acrylate.
7. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 6, it is characterised in that step adds in (4) The mass ratio of existing material is 7:(2-4 to the quality of the resin entered with reactor).
8. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 6, it is characterised in that step adds in (4) In the resin entered, the volume ratio of urethane acrylate, urethane acrylate, epoxy acrylate and polyester acrylate is (1.5-2.5): (1-2): (1.5-2.5): 1.
9. the preparation method of the light-sensitive material containing PVC and PS as claimed in claim 2, it is characterised in that step adds in (4) The temperature of thermal agitation still is 53-67 DEG C, and the rotating speed of stirring is 85-115 rev/min, and mixing time is 8-16 hour.
10. the preparation method of the light-sensitive material containing PVC and PS as described in claim 2-9 is arbitrary, it is characterised in that step (1) in, the volume mixture ratio of 5 kinds of monomers is 2:2:1:3:1;
Urethane acrylate, urethane acrylate, epoxy acrylate and polyester in the resin added in step (4) The volume ratio of acid esters is 2:1.5:2:1.
CN201610613011.6A 2016-07-28 2016-07-28 A kind of light-sensitive material containing PVC and PS and preparation method thereof Pending CN106118036A (en)

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Application Number Priority Date Filing Date Title
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0726062A (en) * 1993-07-15 1995-01-27 Teijin Seiki Co Ltd Resin composition for optical three-dimensional shaping
CN1099047A (en) * 1994-06-27 1995-02-22 北京市富通光电工程公司 Compositions of ultraviolet curing type
JP2008174720A (en) * 2006-10-10 2008-07-31 Dsm Ip Assets Bv Radiation curable matrix composition
CN101495561A (en) * 2006-08-02 2009-07-29 超科有限公司 Photo-crosslinkable polyolefin compositions
US20100256255A1 (en) * 2009-04-07 2010-10-07 Charles Stevens Jettable ink composition
CN105131201A (en) * 2015-09-21 2015-12-09 东莞市盟大塑化科技有限公司 UV (ultraviolet)-curable photosensitive material and application thereof to photocuring 3D printer
CN105189092A (en) * 2013-03-15 2015-12-23 3D系统公司 Three dimensional printing material system
CN105259736A (en) * 2015-11-10 2016-01-20 上海移石新材料科技有限公司 Photosensitive resin for 3D printer and preparation method of photosensitive resin

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0726062A (en) * 1993-07-15 1995-01-27 Teijin Seiki Co Ltd Resin composition for optical three-dimensional shaping
CN1099047A (en) * 1994-06-27 1995-02-22 北京市富通光电工程公司 Compositions of ultraviolet curing type
CN101495561A (en) * 2006-08-02 2009-07-29 超科有限公司 Photo-crosslinkable polyolefin compositions
JP2008174720A (en) * 2006-10-10 2008-07-31 Dsm Ip Assets Bv Radiation curable matrix composition
US20100256255A1 (en) * 2009-04-07 2010-10-07 Charles Stevens Jettable ink composition
CN105189092A (en) * 2013-03-15 2015-12-23 3D系统公司 Three dimensional printing material system
CN105131201A (en) * 2015-09-21 2015-12-09 东莞市盟大塑化科技有限公司 UV (ultraviolet)-curable photosensitive material and application thereof to photocuring 3D printer
CN105259736A (en) * 2015-11-10 2016-01-20 上海移石新材料科技有限公司 Photosensitive resin for 3D printer and preparation method of photosensitive resin

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Application publication date: 20161116