CN108559425B - Solvent-free adhesive for preventing warping of FDM printing device, printing platform and manufacturing method of solvent-free adhesive - Google Patents
Solvent-free adhesive for preventing warping of FDM printing device, printing platform and manufacturing method of solvent-free adhesive Download PDFInfo
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- CN108559425B CN108559425B CN201810448846.XA CN201810448846A CN108559425B CN 108559425 B CN108559425 B CN 108559425B CN 201810448846 A CN201810448846 A CN 201810448846A CN 108559425 B CN108559425 B CN 108559425B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
Abstract
The invention belongs to the technical field of fused deposition printing, and discloses a solvent-free adhesive for preventing warping of an FDM printing device, a printing platform and a manufacturing method of the solvent-free adhesive. The adhesive comprises the following components: ethylene glycol diglycidyl ether, isooctyl acrylate, 1, 2-epoxy-4-vinylcyclohexane, stearyl acrylate, acrylic acid, hydroxyethyl acrylate, cetyl acrylate, lauryl acrylate, glycidyl methacrylate, a free radical initiator and an acrylate crosslinking agent. The printing platform comprises an adhesive and a substrate; the adhesive is coated on the substrate. The adhesive disclosed by the invention is extremely low in initial adhesion and peel strength at the temperature of lower than 40 ℃, a printing device is easy to take off from a platform, the adhesive has good bonding capability at high temperature, the printing device is tightly bonded with the platform, and the device is free of warping.
Description
Technical Field
The invention belongs to the field of fused deposition printing technology (FDM), and relates to a solvent-free adhesive for preventing warpage of an FDM printing device, a printing platform and a manufacturing method of the solvent-free adhesive.
Background
The fused deposition printing technology is one of the most widely applied technologies in the field of 3D printing at present, thermoplastic wires are used as raw materials, the wires are heated and melted by a printer to form a melt with certain fluidity, the melt flows out of a nozzle and then is cooled and solidified, and the melt is superposed layer by layer to be printed and formed. However, the thermoplastic wire material is subjected to large thermal shrinkage in the processes of heating, melting, cooling and solidifying, so that the FDM printing device is warped. Generally, by heating the printing platform, reducing the fuse temperature and the platform temperature difference reduces the occurrence of warpage in the 3D print. However, since the thermoplastic filament melt is spread on the printing platform, the filament and the platform will be bonded firmly after cooling, which makes the device difficult to be taken off from the platform after printing.
In order to safely and conveniently take down the printing device from the printing platform, the printing platform is adhered by a masking tape, and the device is directly printed on the surface of the masking tape or a polytetrafluoroethylene coating is coated on the platform. However, the surface of the printing platform is coated with a layer of masking tape, the specific surface area of the masking tape is large, the bonding strength between the device and the masking tape is also large, and the printing device is not easy to take down after cooling. The use of a large pull tab can result in the masking tape breaking, and some of the tape can be stuck to the surface of the device base and difficult to remove. The surface of the printing platform is coated with a polytetrafluoroethylene coating, when wires shrink greatly, a device is difficult to be firmly bonded with the platform in the printing process, and the risk of warping of the device is caused.
The adhesive reported at present is generally low in bonding strength under a high-temperature condition, shrinks along with the adhesive after being cooled, eliminates free volume between interfaces, increases the contact area between the adhesive and a base material, and can be firmly adhered to the surface of an object. The patent application with the application number of 201410719676.6 discloses an acrylate pressure-sensitive adhesive prepared by polymerizing components such as isooctyl acrylate, vinyl acetate, acrylic acid, hydroxyethyl acrylate, methyl methacrylate, N-hydroxymethyl acrylamide, azobisisobutyronitrile and ethyl acetate, wherein the pressure-sensitive adhesive tape can be fully foamed at 130 ℃ to realize bonding with a base material, and in order to reduce the thermal deformation of a 3D printing device, when conventional wires such as polylactic acid, ABS, HIPS and PETG are generally printed in a 3D mode, the temperature of a platform does not exceed 120 ℃, so that the pressure-sensitive adhesive tape is not suitable for 3D printing of the conventional wires. Chinese patent 201410037153.3 discloses a solvent-based pressure-sensitive adhesive prepared from butyl acrylate, isooctyl acrylate, chloroprene, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, glycidyl acrylate and other components, wherein the two pressure-sensitive adhesive products are not adhered together in a room temperature environment, namely the adhesive strength is low in the room temperature environment, but the adhesive strength is low after high-temperature activation, so that the adhesion between a 3D printing device and a printing platform cannot be met, and the solvent-based adhesive is difficult to coat to a high thickness in the process of manufacturing the printing platform. Therefore, the adhesive can not meet the application requirements of high-temperature bonding strength and easy peeling after cooling in FDM printing.
Disclosure of Invention
Based on the defects of the technology, the invention aims to provide a solvent-free adhesive for preventing the warping of an FDM printing device and a preparation method thereof. The adhesive disclosed by the invention can effectively bond a 3D printing device and a printing platform together at high temperature, prevent the FDM printing device from warping due to thermal shrinkage in the slow cooling process and reducing the printing quality, and can be easily taken down in the process of separating the device from the platform after the device is cooled, so that the device damage or the printing platform damage caused by prying by adopting objects such as sharp metal and the like is avoided.
The invention further provides a printing platform for preventing the warping of the FDM printing device. According to the invention, the adhesive is coated on the surface of the gradient heat-shrinkable material, and then the gradient heat-shrinkable material is fixed on the substrate of the platform, so that the printing platform for preventing the warping of the FDM printing device is obtained. The invention adopts the gradient thermal contraction material to effectively reduce the defect of contraction and deformation of the device caused by the inconsistency of the thermal expansion coefficients of the platform and the device when the device is cooled. The printing platform manufactured by the method also has the advantages of convenience in disassembly and low cost.
The purpose of the invention is realized by the following technical scheme:
a solvent-free adhesive for preventing warping of an FDM printing device comprises the following components in parts by weight:
ethylene glycol diglycidyl ether 12 ~ 18
Isooctyl acrylate 8 ~ 14
1, 2-epoxy-4-vinylcyclohexane 11 ~ 15
Octadecyl acrylate 20 ~ 36
Cetyl acrylate 3 ~ 8
Acrylic acid lauryl ester 5 ~ 12
Free radical initiator 0.3 ~ 0.6.6
Additive 0.7 ~ 2.4.2.4.
The free radical initiator is more than one of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile, preferably more than one of cyclohexanone peroxide or dibenzoyl peroxide.
The additive is more than one of hydrogenated tallow primary amine, erucic amide, caprolactam, polyether amine D-2000, arundoin, stearic acid amide and zinc stearate. The added lubricant can improve the crosslinking degree and the cohesion of the adhesive and improve the bonding strength of the adhesive under a high-temperature condition.
The preparation method of the solvent-free adhesive for preventing the warping of the FDM printing device comprises the following steps:
(1) under the atmosphere of protective gas, uniformly mixing isooctyl acrylate, acrylic acid, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate to obtain a mixture, wherein the uniform mixing in the step (1) refers to uniformly stirring at a low speed of 40 ~ 70 ℃, and the rotating speed of the low-speed stirring is 20 ~ 100 rpm;
(2) dropwise adding a mixed solution prepared from a free initiator and ethylene glycol diglycidyl ether into the mixture under the stirring condition, wherein the temperature of the system does not exceed 80 ℃ in the dropwise adding process, heating to 85 ~ 88 ℃ after the dropwise adding is finished, and continuously reacting to obtain a product A, wherein the stirring rotating speed in the step (2) is 200 ~ 300 revolutions per minute, the dropwise adding speed is 0.1 ~ 0.25.25 unit weight per minute, and the continuous reacting time is 60 ~ 120min, wherein the unit weight refers to the weight unit of each component;
(3) and (3) dropwise adding a mixture of hydroxyethyl acrylate and glycidyl methacrylate into the product A, preserving the heat at 85-88 ℃ for 240 ~ 300min after dropwise adding, then adding additives in batches, and continuously stirring to obtain the solvent-free adhesive, wherein the dropwise adding speed in the step (3) is 0.05 ~ 0.19.19 unit weight/min.
The number of times of batch addition in the step (3) is 3 ~ 5, the time of continuous stirring is 30 ~ 60min, the stirring is stopped when no particles exist in the system, and the cross-linking agent is required to be added dropwise within 30 min.
And (4) after the continuous stirring in the step (3), cooling to 40 ℃, filtering and discharging to obtain the solvent-free adhesive for preventing the warping of the FDM printing device.
The solvent-free adhesive for preventing the warping of the FDM printing device adopts the components such as isooctyl acrylate, glycidyl methacrylate, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate as comonomers, after the monomers are polymerized, the stripping performance of the adhesive at room temperature is improved through the crystallinity of the long flexible chain segment at room temperature, and under the heating condition, the components can be subjected to crystal melting to obtain higher bonding strength again, so that the printing device is firmly bonded with a platform.
The invention adopts ethylene glycol diglycidyl ether to dissolve the free radical initiator (such as benzoyl peroxide), and overcomes the defect that the initiator introduced by adopting comonomers such as hydroxyethyl acrylate and the like to dissolve the free radical initiator in the conventional method is polymerized without being dripped into a reaction kettle. Meanwhile, the ethylene glycol diglycidyl ether is grafted to the molecular structure of the adhesive through the reaction of acrylic acid and epoxy groups, so that the crystallization effect of the adhesive at room temperature is improved, and the strippability of the adhesive at room temperature is improved.
The solvent-free adhesive for preventing the warping of the FDM printing device is used for preparing a printing platform for preventing the warping of the FDM printing device.
The printing platform comprises an adhesive and a substrate, wherein the adhesive is coated on the substrate under a heating condition, the adhesive is a solvent-free adhesive for preventing the warpage of an FDM printing device, the heating temperature is 30 ~ 90 ℃, the substrate is glass, stainless steel or a plastic plate, preferably a plastic plate, the plastic plate is Polycarbonate (PC), polyethylene terephthalate (PET), Polyethylene (PE), poly (butadiene-styrene-Acrylonitrile) (ABS), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG) or Polystyrene (PS), in order to match the thermal shrinkage proportion of a printing piece, a thermal shrinkage coefficient gradient material needs to be set between the adhesive and the platform to prevent the defect that the device deforms due to the large thermal shrinkage difference between the device and the platform, and the thermal shrinkage coefficient gradient material is the plastic plate.
The substrate is arranged on a supporting device or a conventional printing platform, and the substrate can be detached from the supporting device and the printing platform.
When the substrate is arranged on the platform, the printing platform comprises the platform, the substrate arranged on the platform and the adhesive coated on the substrate.
The method for preventing the warping of the FDM printing device comprises the following steps:
(a) coating a heated adhesive on the fixed substrate to obtain a printing platform;
(b) heating the printing platform, enabling the printing device to fall into the printing platform, and bonding the printing device and the printing platform; and then cooling to the normal temperature, and taking down the printing device.
The temperature of the heating in the step (a) is 30 ~ 90 ℃;
the temperature of the heating in step (b) was 50 ~ 110 ℃.
According to the printing platform for preventing the warping of the FDM printing device, the thickness of the solvent-free adhesive is selected according to the size of the printing device and the number of times of use, and preferably, the thickness of the solvent-free adhesive is 0.08 ~ 0.3.3 mm.
In the preparation of the printing platform, after the adhesive is coated on the plastic plate, the other surface of the adhesive needs to be covered by release paper, so that the adhesive is prevented from being polluted; and then fixing the plastic plate coated with the adhesive on a toughened glass plate or a stainless steel plate to manufacture the FDM printing platform. When the device is used, the release paper is peeled off, the heating platform and the printing device fall into the printing platform.
Compared with the prior art, the invention has the following effects:
the anti-warping solvent-free adhesive for the FDM printing device has extremely low initial adhesion and peel strength at the temperature of lower than 40 ℃, ensures that the FDM printing device can be easily taken off from a platform, has good adhesive capacity at the temperature of 50 ~ 110 ℃, and can tightly adhere a thermoplastic printing material which is fused and printed by FDM to the printing platform in the printing process.
Drawings
FIG. 1 is a schematic view of a printing platform (when unprinted) of example 1; 1-glass plate or steel plate, 2-plastic plate, 3-adhesive and 4-release paper.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A solvent-free adhesive for preventing warping of an FDM printed polylactic acid device comprises the following components in parts by weight:
ethylene glycol diglycidyl ether 18
Acrylic acid isooctyl ester 14
1, 2-epoxy-4-vinylcyclohexane 12
Octadecyl acrylate 20
Hydroxyethyl acrylate 5
Acrylic acid cetyl ester 8
Acrylic acid lauryl ester 12
Glycidyl methacrylate 6
Dibenzoyl peroxide 0.3
Erucamide 0.7.
The preparation method of the solvent-free adhesive for preventing the warping of the FDM printed polylactic acid device comprises the following steps:
(1) under the atmosphere of nitrogen, uniformly stirring isooctyl acrylate, acrylic acid, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate at a low speed of 70 ℃ to obtain a mixture; the rotating speed of the low-speed stirring is 60 rpm;
(2) dripping a mixed solution prepared from benzoyl peroxide and ethylene glycol diglycidyl ether into the mixture under the stirring condition of 200rpm, wherein the temperature of the system does not exceed 80 ℃ in the dripping process; after the dripping is finished, heating to 85 ℃, and continuing to react for 120min to obtain a product A; the dropping speed is 90min, and 18.3 parts by weight of the mixed solution is dropped;
(3) dropwise adding a mixture of hydroxyethyl acrylate and glycidyl methacrylate into the product A, preserving the temperature at 85-88 ℃ for 240min after dropwise adding, then adding additives in batches (adding erucamide three times every 10 min), continuously stirring for 10min, cooling to 40 ℃, filtering and discharging to obtain the solvent-free adhesive for preventing the warping of the FDM printed polylactic acid device; the dropping was completed at a rate of 11 parts by weight of the mixture for 60 min.
The solvent-free adhesive is coated on a PC plastic plate and cooled for 30 minutes, the solvent-free adhesive is combined with a toughened glass plate and placed on a printing base to form a printing platform, the thickness of dry adhesive is 0.08 mm, the printing platform is heated to 50 ℃, an FDM printing polylactic acid device (a thin plate with the thickness of 1 cm and the dimension of 150 x 150 mm) is bonded with the adhesive, and the device is cooled and peeled. The sheet with a thickness of 1 cm and a dimension of 150 x 150 mm was not warped. Test results were obtained using ASTM D1876-08 Standard: the peel strength at the polylactic acid interface at room temperature was only 0.1N/2.5 cm, and the peel strength at the polylactic acid interface at 50 ℃ was 10.5N/2.5 cm.
The schematic diagram of the printing platform of the embodiment is shown in fig. 1; 1-glass plate or steel plate, 2-plastic plate, 3-adhesive and 4-release paper. After the adhesive is coated on the plastic plate, the other surface of the adhesive needs to be covered by release paper, so that the adhesive is prevented from being polluted; and then fixing the plastic plate coated with the adhesive on a toughened glass plate or a stainless steel plate to manufacture the FDM printing platform. When the device is used, the release paper is peeled off, the heating platform and the printing device fall into the printing platform.
Example 2
A solvent-free adhesive for preventing warpage of an FDM printed ABS device comprises the following components in parts by weight:
ethylene glycol diglycidyl ether 12
Acrylic acid isooctyl ester 10
1, 2-epoxy-4-vinylcyclohexane 15
Octadecyl acrylate 31
Acrylic acid 8
Hydroxyethyl acrylate 3
Acrylic acid cetyl ester 5
Acrylic acid lauryl ester 8
Glycidyl methacrylate 6
Cyclohexanone peroxide 0.4
Stearic acid amide 1.6.
The preparation method of the solvent-free adhesive for preventing warping of the FDM printed ABS device comprises the following steps:
(1) under the atmosphere of nitrogen, uniformly stirring isooctyl acrylate, acrylic acid, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate at a low speed of 70 ℃ to obtain a mixture; the rotating speed of the low-speed stirring is 60 rpm;
(2) dropwise adding a mixed solution prepared from cyclohexanone peroxide and ethylene glycol diglycidyl ether into the mixture under the stirring condition of 200rpm, wherein the temperature of the system does not exceed 80 ℃ in the dropwise adding process; after the dripping is finished, heating to 85 ℃, and continuing to react for 120min to obtain a product A; the dropping speed is 90min, and 12.4 parts by weight of the mixed solution is dropped;
(3) dropwise adding a mixture of hydroxyethyl acrylate and glycidyl methacrylate into the product A, preserving heat for 240min at 85-88 ℃ after dropwise adding, then adding additives in batches (adding stearic acid amide three times every 10 min), continuously stirring for 10min, cooling to 40 ℃, filtering and discharging to obtain the solvent-free adhesive for preventing warpage of the FDM printed ABS device; the dropping was completed at a rate of 9 parts by weight of the mixture for 60 min.
The solvent-free adhesive is coated on a PET plastic plate and cooled for 30 minutes, the solvent-free adhesive is combined with a toughened glass plate and placed on a printing base to form a printing platform, the thickness of dry adhesive is 0.08 mm, the printing platform is heated to 80 ℃, an FDM printing ABS device (a thin plate with the thickness of 1 cm and the dimension of 150 x 150 mm) is bonded with the adhesive, and the device is cooled and peeled. The sheet with a thickness of 1 cm and a dimension of 150 x 150 mm was not warped. Test results were obtained using ASTM D1876-08 Standard: the peel strength at room temperature was only 0.8N/2.5 cm at the ABS interface and 14.5N/2.5cm at 50 ℃.
Example 3
A solvent-free adhesive for preventing warping of an FDM printing PETG device comprises the following components in parts by weight:
ethylene glycol diglycidyl ether 12
Iso-octyl acrylate 11
1, 2-epoxy-4-vinylcyclohexane 14
Octadecyl acrylate 31
Acrylic acid 7
Hydroxyethyl acrylate 5
Acrylic acid cetyl ester 3
Acrylic acid lauryl ester 8
Glycidyl methacrylate 6
Dibenzoyl peroxide 0.6
Hydrogenated tallow primary amine 2.4.
The preparation method of the solvent-free adhesive for preventing warping of the FDM printed PETG device comprises the following steps:
(1) under the atmosphere of nitrogen, uniformly stirring isooctyl acrylate, acrylic acid, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate at a low speed of 70 ℃ to obtain a mixture; the rotating speed of the low-speed stirring is 60 rpm;
(2) under the condition of stirring at 200rpm, dropwise adding a mixed solution prepared from dibenzoyl peroxide and ethylene glycol diglycidyl ether into the mixture, wherein the temperature of the system does not exceed 80 ℃ in the dropwise adding process; after the dripping is finished, heating to 85 ℃, and continuing to react for 120min to obtain a product A; the dropping speed is 90min, and 12.6 parts by weight of the mixed solution is dropped;
(3) dropwise adding a mixture of hydroxyethyl acrylate and glycidyl methacrylate into the product A, preserving heat at 88 ℃ for 240min after dropwise adding, then adding additives in batches (adding hydrogenated tallow primary amine three times every 10 min), continuously stirring for 10min, cooling to 40 ℃, filtering and discharging to obtain the solvent-free adhesive for preventing the warping of the FDM printing PETG device; the dropping was completed at a rate of 11 parts by weight of the mixture for 60 min.
The solvent-free adhesive is coated on a PS plastic plate and cooled for 30 minutes, the solvent-free adhesive is combined with a toughened glass plate and placed on a printing base to form a printing platform, the thickness of dry adhesive is 0.08 mm, the printing platform is heated to 100 ℃, a PETG device (thin plate with the thickness of 1 cm and the dimension of 150 x 150 mm) is printed by FDM, and the device is bonded with the adhesive, cooled and stripped. The sheet with a thickness of 1 cm and a dimension of 150 x 150 mm was not warped. Test results were obtained using ASTM D1876-08 Standard: the peel strength at room temperature on the PETG side was only 1.0N/2.5 cm, and at 50 ℃ on the PETG interface was 9.5N/2.5 cm.
Example 4
A solvent-free adhesive for preventing warping of an FDM printed high-density polyethylene device comprises the following components in parts by weight:
ethylene glycol diglycidyl ether 15
Acrylic acid isooctyl ester 8
1, 2-epoxy-4-vinylcyclohexane 11
Octadecyl acrylate 36
Acrylic acid 11
Acrylic acid cetyl ester 8
Acrylic acid lauryl ester 5
Azobisisobutyronitrile 0.6
And 2.4 of zinc stearate.
The preparation method of the solvent-free adhesive for preventing the warping of the FDM printed PE device comprises the following steps:
(1) under the atmosphere of nitrogen, uniformly stirring isooctyl acrylate, acrylic acid, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate at a low speed of 70 ℃ to obtain a mixture; the rotating speed of the low-speed stirring is 60 rpm;
(2) dropwise adding a mixed solution prepared from azobisisobutyronitrile and ethylene glycol diglycidyl ether into the mixture under the stirring condition of 200rpm, wherein the temperature of the system does not exceed 80 ℃ in the dropwise adding process; after the dripping is finished, heating to 85 ℃, and continuing to react for 120min to obtain a product A; 15.6 parts by weight of the mixed solution is dropwise added at the dropping speed of 90 min;
(3) dropwise adding a mixture of hydroxyethyl acrylate and glycidyl methacrylate into the product A, preserving heat at 85-88 ℃ for 240min after dropwise adding, then adding additives in batches (adding zinc stearate in three times every 10 min), continuously stirring for 10min, cooling to 40 ℃, filtering and discharging to obtain the solvent-free adhesive for preventing the warping of the FDM printing PE device; the dropping speed was 3 parts by weight of the mixture after completion of dropping for 60 min.
The solvent-free adhesive is coated on a PE plastic plate and cooled for 30 minutes, the solvent-free adhesive is combined with a toughened glass plate and placed on a printing base to form a printing platform, the thickness of dry adhesive is 0.08 mm, the printing platform is heated to 50 ℃, an FDM printing PE device (a thin plate with the thickness of 1 cm and the dimension of 150 x 150 mm) is bonded with the adhesive, and the device is cooled and peeled. The sheet with a thickness of 1 cm and a dimension of 150 x 150 mm was not warped. Test results were obtained using ASTM D1876-08 Standard: the peel strength at room temperature at the high density polyethylene interface was only 0.4N/2.5cm, and at 50 ℃ at the high density polyethylene interface was 12.0N/2.5 cm.
Claims (10)
1. The solvent-free adhesive for preventing warping of FDM printing devices is characterized in that: the paint comprises the following components in parts by weight:
ethylene glycol diglycidyl ether 12 ~ 18
Isooctyl acrylate 8 ~ 14
1, 2-epoxy-4-vinylcyclohexane 11 ~ 15
Octadecyl acrylate 20 ~ 36
Acrylic acid 4 ~ 11
Hydroxyethyl acrylate 1 ~ 5
Cetyl acrylate 3 ~ 8
Acrylic acid lauryl ester 5 ~ 12
Glycidyl methacrylate 2 ~ 6
Free radical initiator 0.3 ~ 0.6.6
Additive 0.7 ~ 2.4.4;
the additive is more than one of hydrogenated tallow primary amine, erucic amide, caprolactam, polyether amine D-2000, arundoin, stearic acid amide and zinc stearate.
2. The solvent-free adhesive for preventing warping of an FDM printing device as claimed in claim 1, wherein: the free radical initiator is more than one of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile.
3. The preparation method of the solvent-free adhesive for preventing warping of the FDM printing device according to any one of claims 1 ~ 2, wherein the preparation method comprises the following steps:
(1) under the atmosphere of protective gas, uniformly mixing isooctyl acrylate, acrylic acid, 1, 2-epoxy-4-vinylcyclohexane, octadecyl acrylate, hexadecyl acrylate and lauryl acrylate to obtain a mixture;
(2) under the condition of stirring, dropwise adding a mixed solution prepared from a free initiator and ethylene glycol diglycidyl ether into the mixture, wherein the temperature of the system does not exceed 80 ℃ in the dropwise adding process, heating to 85 ~ 88 ℃ after dropwise adding, and continuing to react to obtain a product A;
(3) and dropwise adding a mixture of hydroxyethyl acrylate and glycidyl methacrylate into the product A, preserving the heat at 85-88 ℃ for 240 ~ 300min after dropwise adding, then adding additives in batches, and continuously stirring to obtain the solvent-free adhesive.
4. The method for preparing the solvent-free adhesive for preventing warping of the FDM printing device as claimed in claim 3, wherein the step (1) of uniformly mixing is to uniformly stir at a low speed of 40 ~ 70 ℃;
the stirring speed in the step (2) is 200 ~ 300 rpm, and the continuous reaction time is 60 ~ 120 min;
the number of times of adding in batches in the step (3) is 3 ~ 5, and the time of continuing stirring is 30 ~ 60 min.
5. The application of the non-solvent type adhesive for preventing the warping of the FDM printing device as claimed in claim 1 ~ 2, wherein the non-solvent type adhesive for preventing the warping of the FDM printing device is used for preparing a printing platform for preventing the warping of the FDM printing device.
6. Use according to claim 5, characterized in that: the printing platform comprises an adhesive and a substrate; the adhesive is coated on the substrate under the heating condition; the adhesive is a solvent-free adhesive for preventing the warping of the FDM printing device.
7. Use according to claim 6, characterized in that: the substrate is glass, stainless steel or a plastic plate; the substrate is arranged on a supporting device or a conventional printing platform, and the substrate can be detached from the supporting device and the printing platform.
8. Use according to claim 7, characterized in that: the plastic plate is polycarbonate, polyethylene terephthalate, polyethylene, poly (butadiene-styrene-acrylonitrile), polyethylene terephthalate-1, 4-cyclohexanedimethanol ester or polystyrene.
9. A method for preventing warping of an FDM printing device is characterized by comprising the following steps of (a) coating heated adhesive on a fixed substrate to obtain a printing platform, (b) heating the printing platform, enabling the printing device to fall into the printing platform, enabling the printing device to be bonded with the printing platform, cooling to the normal temperature, and taking down the printing device, wherein the printing platform is defined in any one of claims 5 ~ 8.
10. The method of claim 9, wherein the heating temperature in step (a) is 30 ~ 90 ℃ and the heating temperature in step (b) is 50 ~ 110 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN109628023A (en) * | 2018-11-13 | 2019-04-16 | 桐乡市星邦科技发展有限公司 | A kind of acryloid cement gold stamping for casement and preparation method thereof |
| CN111331132A (en) * | 2020-03-17 | 2020-06-26 | 苏州复浩三维科技有限公司 | 3D printing method |
| CN115368851B (en) * | 2021-12-17 | 2024-03-22 | 湖州绿田新材料有限公司 | Acrylic adhesive and application thereof |
| CN115368852B (en) * | 2021-12-17 | 2024-03-26 | 湖州绿田新材料有限公司 | Ultra-high temperature resistant protective film adhesive and preparation method thereof |
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| CN102399499A (en) * | 2010-09-01 | 2012-04-04 | 日东电工株式会社 | Temporary fixing sheet |
| CN105073932A (en) * | 2013-04-05 | 2015-11-18 | 霓达株式会社 | Temporary fixing double-sided adhesive tape and temporary fixing method for workpiece using same |
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